JPH0584283A - Deodorants - Google Patents

Abstract

(57) [Summary] [Structure] This deodorant is represented by the formula: HOOC-A-COOH [I] [wherein A represents a divalent hydrocarbon residue having 2 to 6 carbon atoms]. At least one copper salt selected from copper (II) salts of organic dicarboxylic acids. Further, it is a deodorant containing a free organic carboxylic acid and a porous carrier. [Effect] The deodorant of the present invention has an excellent effect on a complex odor composed of hydrogen sulfide, mercaptans, ammonia and the like. Moreover, this deodorant is excellent in moldability.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel deodorant. The present invention also relates to a novel deodorant that is familiar to daily life such as body odor and indoor odor, and is effective for deodorizing complex odors that are composed of many odor components and are very difficult to deal with.

[0002]

2. Description of the Related Art Conventionally, as a method for reducing a malodorous component, an adsorption method using a porous adsorbent such as activated carbon, alumina, zeolite, a catalytic combustion method, an oxidation method using ozone, a neutralization method using a chemical, or A method of decomposing with bacteria is known. However, in the case of the adsorption method using an adsorbent, the adsorption capacity is small and the adsorption rate is slow. In addition, the catalytic combustion method, the oxidation method using ozone, or the bacterial decomposition method requires complicated equipment and high running costs. Furthermore, the neutralization method of neutralizing with a chemical has a relatively small deodorizing capacity.

Various metal compounds have hitherto been used as deodorants for improving such drawbacks, especially as deodorants for acidic odors of sulfur compounds such as hydrogen sulfide and mercaptans. However, these metal compounds generally have no deodorizing effect on basic odors such as ammonia and amines. On the other hand, a carboxylic acid-containing polymer compound that is effective for deodorizing a basic odor component usually does not exhibit deodorizing ability for an acidic odor.

However, the familiar malodors that are actually a problem in daily life are not only acidic odors and basic odors but also complex odors composed of various components such as aldehydes and lower fatty acids. Therefore, in order to deodorize these complex odors, it is necessary to combine and use substances that are effective against individual malodorous components, and a multifunctional deodorant in which they are integrated is desirable.

As such a deodorant, for example, Japanese Patent Laid-Open No.
JP-A-2-34565 discloses a deodorant in which at least one of a zinc compound and a copper (II) compound is used as an active ingredient, and the active ingredient is attached to a porous carrier such as zeolite or activated carbon. However, all the compounds of the invention are water-soluble and are neutralizing deodorants that neutralize and deodorize hydrogen sulfide and mercaptans in an aqueous solution. Further, Japanese Patent Application Laid-Open No. 52-32893 discloses the removal of ammonia, but here again only the method of using an aqueous solution of polybasic acid such as fumaric acid is disclosed. Further, this method cannot satisfactorily achieve the removal of hydrogen sulfide, mercaptan, and the like.

Further, JP-A-63-41408 discloses a deodorant / bactericidal / antifungal composition comprising a copper compound, an oxocarboxylic acid compound and water. However, although the effect in an aqueous solution has been recognized, it is not yet satisfactory as a practical deodorant.

[0007]

The object of the present invention is to eliminate complex odors, particularly hydrogen sulfide and mercaptans, by catalytically oxidizing them with oxygen in the air to deodorize them. Another object of the present invention is to provide a new deodorant that is also effective for deodorizing basic odors such as ammonia. Another object of the present invention is to provide a novel deodorant which can be molded into a form that can be sufficiently contacted with the atmosphere containing odors and can sufficiently exhibit its original deodorant activity.

[0008]

Means for Solving the Problems The present inventor has made various studies in order to solve the above problems. As a result, the inventors have found that a specific copper salt of an organic dicarboxylic acid exhibits an excellent deodorizing effect on complex odors, and further research has been completed to complete the present invention.

The present invention provides an organic dicarboxylic acid copper (II) represented by the formula: HOOC-A-COOH [I] [wherein A represents a divalent hydrocarbon residue having 2 to 6 carbon atoms]. ) A deodorant containing a salt is provided.

In the present invention, the acid used to form the copper salt is an organic dicarboxylic acid. Such an organic dicarboxylic acid is represented by the above formula [I]. In the formula, A is a divalent hydrocarbon residue having 2 to 6 carbon atoms. The hydrocarbon residue may be a divalent chain or cyclic aliphatic hydrocarbon residue or a divalent aromatic hydrocarbon residue.

Examples of the divalent chain aliphatic hydrocarbon residue include saturated chain aliphatic hydrocarbon residues such as alkylene and unsaturated chain aliphatic hydrocarbon residues such as alkenylene. Preferred are alkylene and alkenylene having 2 to 6 carbon atoms.

Examples of the divalent cycloaliphatic hydrocarbon residue include cyclohexylene, tetrahydrophenylene, norbornenylene and the like. Preferred is 1,4-cyclohexylene.

Examples of the divalent aromatic hydrocarbon residue include phenylene and naphthylene. Preferably m
-Or p-phenylene group.

Furthermore, A is a lower alkyl group (having 1 to 1 carbon atoms).
4) or a hydroxyl group may be substituted. Of the above, alkylene and alkenylene are particularly preferable.

Specific examples of the organic dicarboxylic acid represented by the formula [I] include saturated aliphatic dicarboxylic acids (malonic acid, succinic acid, glutaric acid, adipic acid, etc.) and unsaturated aliphatic dicarboxylic acids (fumaric acid). Acid, maleic acid, mesaconic acid, etc.), aromatic dicarboxylic acid (isophthalic acid, terephthalic acid, etc.), saturated cyclic dicarboxylic acid (1,4- or 1,
2-cyclohexanedicarboxylic acid, etc.), unsaturated cyclic dicarboxylic acids (tetrahydrophthalic acid, hymic acid, etc.) and the like. Of the above organic dicarboxylic acids, fumaric acid, maleic acid, mesaconic acid, succinic acid, and adipic acid are preferable, and fumaric acid is particularly preferable from the viewpoint of moldability.

The copper (II) salts of these organic dicarboxylic acids show a catalytic action to oxidatively deodorize hydrogen sulfide and mercaptans, and show a large deodorizing capacity. These organic dicarboxylic acid copper salts may be used alone or in admixture of two or more.

Further, by adding a free organic carboxylic acid in addition to these organic dicarboxylic acid copper salts, the deodorant of the present invention exhibiting an excellent deodorizing effect not only on acidic odor but also on basic odor. Is obtained.

The free organic carboxylic acid is preferably an organic polybasic acid. Among them, they are divalent or trivalent.

The above divalent organic carboxylic acid is represented by the formula: HOOC-A'-COOH [II] [wherein A'means a divalent hydrocarbon residue having 2 to 6 carbon atoms]. To be done. A'shown here is A in the above formula [I].
Is synonymous with. Further, specifically, the above-mentioned organic dicarboxylic acid may be mentioned.

The above-mentioned trivalent organic carboxylic acid is preferably aliphatic (citric acid, etc.) or aromatic (hemimellitic acid, trimellitic acid, trimesic acid, 1,2,4,5-benzenetetracarboxylic acid, etc.). ..

Among the above, divalent organic carboxylic acid is particularly preferable.

The free organic carboxylic acid used may be the free organic dicarboxylic acid corresponding to the compounded organic dicarboxylic acid copper salt, or may be a different type of free organic carboxylic acid. Two or more kinds of these free organic carboxylic acids may be used.

These free organic carboxylic acid or organic dicarboxylic acid copper salts preferably have low solubility in water in terms of moldability. For example, the solubility in 100 g of water at 25 ° C. is 1 g or less.

The mixing ratio of the organic dicarboxylic acid copper salt and the free organic carboxylic acid is 3: 0.2 to 10 by weight, preferably 3: 0.5 to 5.

Furthermore, by using a porous adsorbent in combination with these organic dicarboxylic acid copper salt and free organic carboxylic acid, it has excellent moldability and has a strong and quick deodorizing effect on complex odors. A deodorant is obtained.

The organic dicarboxylic acid copper salt or the free organic carboxylic acid may be in the form of powder or granules. In this case, the particle size is not particularly limited, but the average particle size is 10 mesh or less, preferably 16 to 32.
The range is 5 mesh, more preferably 32 to 100 mesh. In order to mix and mold with other powders (such as a porous adsorbent), it is preferable to use a powdery powder of 100 mesh or less. In particular, fine particles are preferable for mixing and molding.

The porous adsorbent used in the deodorant of the present invention includes an inorganic porous material and an organic porous material.

Examples of the inorganic porous substance include activated carbons (activated carbon, activated carbon fibers, etc.), silica gel type (silica gel, silica / alumina, silica / magnesia etc.), alumina type (alumina etc.), clay (alumina boria). Acid clay, activated clay, etc., natural siliceous materials (sepiolite,
Palygorskite, natural and synthetic zeolites, vermiculite, etc., various synthetic silicates, various synthetic aluminosilicates (Mizucanite (trade name), Mizuka Life (trade name)
Etc.), others (phosphate silicate, aluminum phosphate,
Titanium phosphate, diatomaceous earth, etc.).

The organic porous material is a polymer porous material or the like.

The particle size of such a porous adsorbent is appropriately determined.
It may be selected depending on the purpose of use, but in order to mix / mold with the organic dicarboxylic acid copper salt or organic carboxylic acid, 10
It is preferable to use a powdery form of 0 mesh or less. Especially fine particles are preferable.

Of the above adsorbents, activated carbons, particularly activated carbon, are preferred. When using activated carbon, its specific surface area is 200
m ² / g or more, preferably in the range of 500~4000m ² / g, more preferably 600~3600m ² / g.

Among the above-mentioned porous adsorbents, those having a low solubility in water also have a function as a carrier for an organic dicarboxylic acid copper salt or a free organic carboxylic acid and are preferable for forming a molded article. Activated carbon is also preferable for this purpose.

Further, pulp, fibers, cloth and paper (including sepiolite mixed paper), etc., which have no adsorption ability per se or have a low adsorption ability, may contain organic dicarboxylic acid copper salt or free organic carboxylic acid. It is effectively used as a carrier.

In the preparation of the deodorant of the present invention, the above-mentioned organic dicarboxylic acid copper salt may be prepared in advance by a known method, and the organic decarboxylic acid copper salt may be prepared by a chemical reaction in a system for preparing the deodorant. A copper compound from which a dicarboxylic acid copper salt is obtained may be used as a starting material.

In order for the deodorant of the present invention to exhibit a strong and wide range of deodorizing activity, it is preferable to mix the above-mentioned organic dicarboxylic acid copper salt, free organic carboxylic acid and activated carbon in a fixed ratio. The mixing ratio of these is 3: 0.2 by weight.
It is 5: 1 to 20, preferably 3: 0.5 to 3: 2 to 5.

In order to mold the deodorant of the present invention, an appropriate amount of water of 40 to 75 parts by weight, preferably 50 to 60 parts by weight, is added to 100 parts by weight of the solid content when the respective components are mixed. preferable. Further, other molding aids such as carboxymethyl cellulose and biopoly (trade name: Takeda Pharmaceutical Co., Ltd.
(Manufactured by Co., Ltd.) and the like may be added and the mixture may be molded. After molding,
It can be dried and pulverized to give a powdery or granular composite deodorant. Further, the deodorant of the present invention can be easily molded into an appropriate shape according to the purpose by a known method such as extrusion molding into a rod shape, a pellet shape, or a honeycomb shape. The molded product is preferably dried appropriately to obtain the final product.

The deodorant thus obtained may be covered with a non-woven fabric, paper or the like to form a bag-shaped or sheet-shaped deodorant. The sheet used for this sheet deodorant material is
A sheet having at least breathability manufactured from fibers such as natural fibers and synthetic fibers is preferable. Further, when removing a liquid odor component, a water-permeable sheet is used. For example, when a non-woven fabric is used, any conventionally known one can be used, and specifically, nylon-6,
Nonwoven fabrics obtained from synthetic fibers such as nylon-6,6, polyester, polyethylene terephthalate, vinylon, polypropylene and polyvinyl alcohol, and natural fibers such as hemp and cotton are mentioned.

Depending on the usage conditions of the deodorant of the present invention, a material having hydrophilicity, water repellency, water permeability, etc. may be used for the sheet to prepare a sheet deodorant suitable for the usage conditions. You can also

The method for holding the deodorant of the present invention between the sheets is not particularly limited. For example, the deodorant is held evenly by sandwiching the deodorant between two sheets and adhering or joining both the sheets. Alternatively, the deodorant may be held by bending one sheet, sandwiching the deodorant in the same way, and joining the upper and lower sheets.

The basis weight of the deodorant in the sheet-shaped deodorant is 3
The amount is 00 g / m ² or less, preferably 10 to 250 g / m ² , and more preferably 15 to 200 g / m ² .

In order to stably hold the deodorant, a method of fixing with an adhesive or the like, a method of forming a bag into a sheet and filling and fixing the deodorant material in its width, or a method of fixing with heat sealing It is preferable to use a method or the like to prepare a sheet deodorant.

[0042]

EXAMPLES Next, the present invention will be described in more detail based on examples.

[Example 1] 10 mg of copper fumarate powder was placed in a mayonnaise bottle having an internal volume of about 925 mL, a resin inner lid provided with a silicone rubber gas inlet was provided, and the periphery of the lid was sealed. A screw lid was formed by hollowing out the part corresponding to the gas inlet from above. Then, the gas to be measured (hydrogen sulfide or methyl mercaptan) was injected by a syringe so that the gas concentration in the mayonnaise bottle would be approximately 100 ppm (almost the same amount of gas in the bottle was taken out with a syringe), and then left at room temperature. did. The gas concentration in the bottle was measured over time by gas chromatography (a gas chromatograph manufactured by Shimadzu Corporation). Every 48 hours after the injection, the gas was replenished again until the gas concentration in the bottle became almost 100 ppm, and the total amount (mg) of the processed gas per unit weight (g) of the sample was determined. The results are shown in Table 1.

Table 1 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Test No. Measurement target gas Test period Total gas throughput (hr) (mg / g) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━ Example 1 Hydrogen sulfide 2369 872 〃 Methyl mercaptan 2827 1108 〃 〃 8209 3877 ─────────────────────────────── ───── Comparative example (activated carbon) Hydrogen sulfide 1175 378 〃 Methyl mercaptan 1197 674 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━

FIG. 1 shows the measurement data of the X-ray diffraction of the sample powder after the hydrogen sulfide gas deodorizing test was conducted on the deodorant of Example 1. From the powder X-ray diffraction chart shown in FIG. 1, a peak indicating the presence of α-sulfur was recognized, and it was found that hydrogen sulfide was oxidized and fixed as sulfur in the deodorant. Therefore, it can be seen that the high treatment capacity of the deodorant of Example 1 is based not only on the stoichiometric reaction but also on the catalytic oxidizing ability. Thus, the copper compound of the deodorant of the present invention has the ability to oxidatively deodorize sulfur-based gas.

[Examples 2 to 18] Copper hydroxide, copper fumarate, fumaric acid, activated carbon, a molding aid (Biopoly (trade name: manufactured by Takeda Pharmaceutical Co., Ltd.)) in the amounts shown in Table 2 below. )
And water were kneaded well. This was extruded using a syringe or a flow tester (CFT500 manufactured by Shimadzu Corporation), dried overnight at 115 ° C., and then pulverized to obtain a deodorant.

[Example 19] The deodorant obtained in Example 18 was pulverized to obtain 500 mg of a 32-100 mesh sieve product. This is made of breathable polypropylene non-woven fabric (9
A sheet-shaped deodorant material was spread on a 5 mm square and a basis weight of 50 g / m ² ) so as to be almost uniform, covered with the same non-woven fabric from above and covered with a heat sealer, and sealed in a square size of 10 mm square. ..

[Example 20] 10 g of fumaric acid (32-40 mesh sieved product), 1.7 g of copper hydroxide and 5 mL of water were kneaded and spread on a petri dish, reacted at 115 ° C for 1 hour and dried. It was The plate-shaped kneaded product obtained is crushed to 30 to 60
5.5 g of the sieved product was obtained. This was treated in the same manner as in Example 19 to obtain a sheet-shaped deodorant material.

[Example 21] Copper fumarate 430 g, activated carbon 325 g, fumaric acid 95 g, organic binder (Metroses <90SH-100,000>: trade name) 25.5 g, Biopoly (trade name: Takeda Pharmaceutical Co., Ltd.) 17 g of water 468 m
It kneaded with L in a kneader for about 2 hours to obtain a clay-like compound. This compound is 30 × 30mm, 30
It was extruded by an extrusion molding machine equipped with a 0-cell square honeycomb mold and dried to obtain a honeycomb deodorant.

Table 2 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example Copper hydroxide Fumarate Copper Fumarate Activated carbon molding aid Water (g) (g) (g) (g) (g) (mL) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━ 2 3 -5 5 0.5 0.5 11 3 1 -3.3 -0.3 3 3 4 3 -1 5 0.5 0.5 14 ────────────── ────────────────────── 5 3−10 5 0.5 13 6 2−2.4 1.8 1.8 0.2 5.4 7 2−10 3.3 0.5 9 8 2 −13.3 3.3 3.3 0.5 9 ─────────────────────────────── ───── 9-4.4-1.8 0.2 5.4 10-3.7 4.3-0.2 3 3 11-3.7 4.3 3.5 0.3 3.8 12-3.7 4. 3.1 0.3 6.6 13-3.7 4.3 3.5 0.4 7.5 ─────────────────────────── ───────── 14-3.7 4.3 4.3 0.5 15.4 15-3.7 4.3 4.3 20 0.8 31.6 16-3.3 3.3 3.3 2.5 0.3 5.6 17-3.3 3.3 3.3 3.3 0.3 5.7 18-4.3 1 3.3 3.3 6.7 ━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━

(Deodorant Test) FIG. 2 is a schematic diagram of an experimental apparatus (circulation method) for evaluating the deodorant performance of the deodorant of the present invention. A mixed odor containing hydrogen sulfide, methyl mercaptan and 10 ppm each of ammonia is prepared in the mixing bottle 1. The mixed odor is sent from the air pump 2 to the glass tube 4 with the plate 3 (inner diameter 10 mm). The glass tube 4 is filled with 1.5 mL of the deodorant 5 of Example 2 or Example 18 (16-22 mesh pulverized product). The mixed odor was sent at a linear velocity of 21 cm / sec (1 L / min), and the concentration of each gas on the outlet side was measured over time. For the measurement, gas chromatography was used for hydrogen sulfide and methyl mercaptan, and a detector tube was used for ammonia.
The gas concentration on the inlet side was measured by sampling from the sampling port 6. The deodorizing performance was evaluated by the residual rate of odor obtained by the following formula.

Residual rate = (C ₁ / C ₀ ) × 100 [where C ₀ is the original gas concentration and C ₁ is the gas concentration after passing through the deodorant sample. The results are shown in Table 3 in comparison with the case of using activated carbon.

Table 3 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Gas residual rate (%) ─── ───────────── Test No. Gas to be measured Elapsed time (hr) 0 50 100 150 150 ━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━ Example 2 Hydrogen sulfide 0 0 2 10 〃 18 〃 0 0 1 3 Comparative example (activated carbon) 〃 0 3 5 8 ─────── ────────────────────────────── Example 2 Methyl mercaptan 0 0 1 8 〃 18 〃 0 0 1 3 Comparative example (activated carbon ) 1 21 22 32 ──────────────────────────────────── Example 2 Ammonia 0 4 40 44 〃 18 〃 0 4 38 52 Comparative Example (Activity Charcoal) 〃 96 87 78 70 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ [Example 22] Activated carbon 19 0.3 g was dispersed in 100 mL of water, and a 40 mL aqueous solution of 2.5 g of copper sulfate pentahydrate was added thereto. On the other hand, a sodium fumarate aqueous solution prepared by adding 20 mL of a 10% sodium hydroxide aqueous solution to a liquid prepared by suspending 1.16 g of fumaric acid in 20 mL of water was added dropwise to the aqueous solution in which activated carbon was dispersed at room temperature. The obtained precipitate was filtered, washed with water, and dried to obtain 19.46 g of activated carbon-copper fumarate composite. When the hydrogen sulfide deodorizing capacity of this composite was measured in the same manner as in Example 1, the gas treatment amount after 3070 hours was 1064 mg / g.

[0054]

The deodorant of the present invention has the ability to oxidatively treat sulfur-based malodorous gases (hydrogen sulfide, methyl mercaptan, etc.). Further, the deodorant compounded with a free organic carboxylic acid and a porous adsorbent has an excellent deodorant performance even for a complex odor containing a basic malodorous gas such as ammonia.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction chart of a deodorant after a deodorant test.

FIG. 2 is an experimental apparatus (circulation method) for evaluating deodorant performance.

[Explanation of symbols]

 1 Mixing bottle 4 Glass tube 5 Deodorant

Claims (4)

[Claims] 1. A copper (II) salt of an organic dicarboxylic acid represented by the formula: HOOC-A-COOH [I] [wherein A represents a divalent hydrocarbon residue having 2 to 6 carbon atoms]. Deodorant containing. 2. The deodorant according to claim 1, wherein the organic dicarboxylic acid is fumaric acid. 3. The deodorant according to claim 1, which further comprises a free organic carboxylic acid and a porous adsorbent. 4. The deodorant according to claim 3, which contains copper fumarate, fumaric acid and activated carbon.