JPH11137657A - Deodorant and deodorant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inexpensive deodorant which exhibits an excellent deodorization performance to many malodorous gases and is easily modable by an arbitrary method by incorporating copper aminochlorotoluenesulfonate into this deodorant. SOLUTION: The deodorant contains the copper aminochlorotoluenesulfonate. The copper aminochlorotoluenesulfonate used in this embodiment may be easily obtd. by reacting aiminochlorotoluenesulfonic acid with copper ions. Namely, the aminochlorotoluenesulfonic acid is dissolved into a solvent, such as water, and thereafter, copper ions are added thereto, by which the hardly water soluble copper aminochlorotoluenesulfonate is rapidly formed. The copper aminochlorotoluenesulfonate is hardly soluble in water, has high reactivity, has the extremely good deodorization performance to many odorous materials including odorous materials of a sulfur system, such as hydrogen sulfide and methyl mercaptan and aldehydes, such as formaldehyde and acetoaldehyde, and is stable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a good deodorant for many odors, and more particularly to a deodorant and a deodorant composition containing copper aminochlorotoluenesulfonate.

[0002]

2. Description of the Related Art As the standard of living increases, there is an increasing interest in odors in many situations, including ordinary life. The most common deodorants are those based on fragrance and activated carbon, but fragrances have a peculiar odor due to their properties, and not only are the places where they can be used limited, but also depending on the conditions of use. Conversely, an aromatic odor may be perceived as offensive. Activated carbon can deodorize over a wide range because it absorbs odor substances in its pores.However, once adsorbed odor substances desorb depending on conditions such as temperature and humidity, and low-molecular weight odors such as ammonia The substance has a drawback that it is difficult to adsorb.

[0003] On the other hand, many deodorants based on a chemical deodorizing effect using metal ions have been proposed, but the chemical deodorizing has a disadvantage that the deodorizing effect is low except for the odors of interest. Copper ion has a very high deodorizing ability against sulfur-containing substances, but has relatively low deodorizing ability against amines and aldehydes, and ferrous ion has a very high deodorizing ability against nitrogen-containing substances. Deodorizing capacity for sulfur substances is relatively low. For example, as a deodorizing method using a transition metal salt of tannic acid, Japanese Unexamined Patent Publication No.
No. 18358, JP-A-1-266275, etc., which show a high deodorizing effect on nitrogen-based malodorous substances such as trimethylamine, but show sulfur-based substances such as hydrogen sulfide and methyl mercaptan. Had a relatively low deodorizing effect on malodorous substances, and a sufficient deodorizing effect could not be obtained depending on the conditions used. In addition, when copper ions and ferrous ions are used in a mixture to make up for the respective disadvantages, the deodorizing functions are offset because of the contradictory deodorizing mechanisms of the reducing action and the oxidizing action, thereby deteriorating the deodorizing ability. Had been brought.

On the other hand, as deodorizing components for aldehydes, JP-A-2-180634 and JP-A-3-296.
434, JP-A-5-23588 and JP-A-6
No. 2,225,927 proposes the use of aromatic amines, but these alone do not provide much deodorizing ability against odorous substances other than aldehydes, and water-soluble copper salts of aromatic amines and iron Even if salt is used in mixture,
It was difficult to prevent the offset effect of copper ions and iron ions.

Further, Japanese Unexamined Patent Publication (Kokai) No. 8-299421 proposes a deodorant gel which is obtained by polymerizing a metal salt of a vinyl compound having a sulfonic acid group to make it insoluble in water. No effect was expected. Also,
Some of them utilize the photocatalytic action of metals such as titanium, but they are generally difficult to use because of their slow deodorizing speed and high cost.

[0006]

Since the number of odorous substances is very large, ordinary deodorants are limited in odors that can be deodorized, for example, for toilets, refrigerators and tobaccos, and are generally used as deodorants. However, for example, in order to use a mixture of copper ions and ferrous ions, it is necessary to acidify the deodorant, so when the carrier is supported by impregnation or the like, Deterioration was easily caused, and the shape of the deodorant was limited to liquid or gel. PH to compensate for these drawbacks
When is made to be neutral to basic, there is a problem that the reactivity is lowered due to the offsetting action of the deodorizing action, and the oxidizing action by oxygen in the air rapidly progresses. An object of the present invention is to provide a stable, efficient and inexpensive deodorant which has a deodorizing effect on many types of malodors and solves the above problem.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, are very inexpensive and have a very wide range of hydrogen sulfide, ammonia, methyl mercaptan, trimethylamine, acetaldehyde and pyridine. The present inventors have found a deodorant capable of removing odorous substances with very high deodorizing power and in a short time, and have completed the present invention. That is, the present invention provides a deodorant containing copper aminochlorotoluenesulfonate, a deodorant using copper aminochlorotoluenesulfonate and ferrous tannate, and a porous carrier carrying these. A deodorant composition is provided.

Hereinafter, the present invention will be described in detail. Copper aminochlorotoluenesulfonate used in the present invention can be easily obtained by reacting aminochlorotoluenesulfonic acid with copper ions. That is, by dissolving aminochlorotoluenesulfonic acid in a solvent such as water and adding copper ions, poorly water-soluble copper aminochlorotoluenesulfonic acid is quickly formed. The composition of the copper salt varies depending on the obtaining method, and the ratio of aminochlorotoluenesulfonic acid to copper is usually 2.5 to 3: 1, but the salt is not limited to this composition ratio.

The aminochlorotoluenesulfonic acid used as a starting material is, for example, 3-amino-6-chlorotoluene-4-sulfonic acid or 4-amino-sulfonic acid which is usually referred to as C acid.
Regardless of the isomer such as 2-chlorotoluene-5-sulfonic acid, the sulfonic acid group in the molecule, such as sodium aminochlorotoluenesulfonate, may form a salt with an alkali metal or ammonium. These aminochlorotoluenesulfonic acids and salts thereof may be used alone or as a mixture.

[0010] The present invention further provides a deodorant containing copper aminochlorotoluenesulfonate and ferrous tannate. The mixing ratio of the two can be freely changed depending on the malodorous component to be deodorized. However, when the content of copper aminochlorotoluenesulfonate is 10% or less, the ability to deodorize sulfur-based malodorous substances such as hydrogen sulfide is reduced.
If it exceeds 5%, the ability to deodorize nitrogen-based malodorous substances such as trimethylamine decreases. Therefore, to deodorize general malodor, iron tannate is preferably used in an amount of 0.10 to 0.25 per 1 part of copper aminochlorotoluenesulfonate.

[0011] The deodorant of the present invention can be used as a deodorant composition by being supported on a porous carrier. Since the deodorant of the present invention is a poorly water-soluble powder, the yield can be freely set even in wet molding which is liable to drop off when metal ions are used as a carrier component, and carboxy may be used if necessary. With a very high yield using binder agents such as methylcellulose and polyvinyl alcohol,
It can be a free-form composition having any composition. The shape, composition, and manufacturing method at this time are not particularly limited as long as they are in accordance with the gist of the present invention.However, since the yield can be improved and a further improvement in the deodorizing effect by adsorption can be expected, a porous material is used. It is particularly preferable to use as a carrier a flexible carrier, particularly a pulp having a high degree of freedom in shape.

The aminochlorotoluenesulfonate copper used in the present invention is poorly water-soluble and highly reactive, and contains hydrogen sulfide,
It has a very good deodorizing ability against many odorous substances including sulfur odorous substances such as methyl mercaptan and aldehydes such as formaldehyde and acetaldehyde. In addition, since it is very stable, the deodorizing performance due to the offsetting action between metal components, which has conventionally occurred when a copper salt and an iron salt are simply used in a mixture, is not reduced. When used in combination with ferrous acid, it has a very good deodorizing ability against nitrogen-based odor substances such as ammonia and trimethylamine in addition to the above-mentioned odor substances. It has become possible to deodorize a wide variety of malodors, which complements the deodorization of low-performance odorous substances.

The deodorant of the present invention can be used by directly mixing with other deodorant components. The highly stable deodorant component of the present invention easily maintains the activity of the other deodorant component, and is hardly affected by the other deodorant component. This is also one of the excellent features of the present invention.

[0014]

EXAMPLES Example 1 Aminochlorotoluenesulfonic acid (4-amino-2-chlorotoluene-5-sulfonic acid: a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was converted to cuprous sulfate (cuprous sulfate / 7 water). Japanese product: Equimolar amount is mixed with boiling point water with a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd., and the resulting suspension is collected by filtration, washed well with boiling water, dried, and aminochloro of yellow-green fine powder is obtained. Copper toluenesulfonate was obtained. A portion of this powder was used to measure the copper content by atomic absorption spectrometry, and the ratio of aminochlorotoluenesulfonic acid to copper was calculated. The ratio of aminochlorotoluenesulfonic acid to copper was 2.5 to 3: 1. It was one.

Example 2 0.9 kg of aminochlorotoluenesulfonic acid (4-amino-2-chlorotoluene-5-sulfonic acid: a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) and cuprous sulfate (cuprous sulfate) 7
1.18 kg of a hydrate (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was mixed in boiling water to obtain a copper aminochlorotoluenesulfonate suspension. Dissolve pulp (DP) having a dry weight of 8 kg and carboxymethylcellulose having a dry weight of 2 kg are thoroughly disintegrated, and the whole amount of the copper suspension of aminochlorotoluenesulfonate is added thereto, mixed well, and pH is adjusted with 120 g / l of sodium hydroxide. The pulp supported with copper aminochlorotoluenesulfonate was obtained by setting the sample to 7. This supported pulp is made into paper,
After drying, a deodorant composition was obtained. The sample had a yellowish-green tint, had no abnormalities on the surface, and had no effect on the pulp as a carrier when dried. When the copper content of this composition was measured by an atomic absorption method, the content of copper was 2.9%.

Example 3 Aminochlorotoluenesulfonic acid (4-amino-2-chlorotoluene-5-sulfonic acid: a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was treated with cuprous sulfate (cuprous sulfate sulfate heptahydrate). The mixture was mixed with boiling point water at a molar ratio of aminochlorotoluenesulfonic acid to copper of 3: 1 to obtain a copper suspension of aminochlorotoluenesulfonic acid. Separately, an excess amount of an aqueous tannic acid solution is added to an aqueous solution of ferrous sulfate (ferrous sulfate heptahydrate: a special-grade reagent manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture is sufficiently stirred to form an iron tannate suspension. Obtained. These two types of suspensions were mixed so that the ratio of the copper metal component to the iron metal component was 9 to 1, stirred, filtered, washed,
Drying was performed to obtain a fine powder deodorant. The fine powder had a slightly green grey.

Example 4 0.81 kg of aminochlorotoluenesulfonic acid (4-amino-2-chlorotoluene-5-sulfonic acid: a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) and cuprous sulfate (cuprous sulfate)
Hexahydrate: Special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) 1.08 kg
Was mixed in boiling water to obtain a copper suspension of aminochlorotoluenesulfonic acid. 8 kg dry pulp (DP)
And 1 kg of dry weight of carboxymethylcellulose were thoroughly disintegrated, and the whole amount of the aminochlorotoluenesulfonate copper suspension was added and mixed well. Pulp was obtained. Separately, ferrous sulfate (ferrous sulfate heptahydrate: a special grade reagent manufactured by Wako Pure Chemical Industries) 0.15k
g and 0.2 kg of tannic acid are defibrated and dry weight 1 k
g of carboxymethylcellulose suspension, and the mixture was allowed to react. Then, the pH was adjusted to 7 with 120 g / l sodium hydroxide to obtain pulp supporting iron tannate. The pulp supporting copper aminochlorotoluenesulfonate and the pulp supporting iron tannate were mixed well, then paper-made and dried to obtain a deodorant composition. Although the composition was grayish, there was no abnormality on the surface, and no effect was observed on the pulp as a carrier when dried. When the copper and iron contents of this composition were measured by the atomic absorption method, it was 2.8% for copper and 0.3% for iron.

Comparative Example 1 An aqueous solution of cuprous sulfate (cuprous sulfate heptahydrate: a special-grade reagent manufactured by Wako Pure Chemical Industries) and ferrous sulfate (ferrous sulfate heptahydrate: Wako Pure Chemical) An aqueous solution of an industrial company (special grade reagent) was mixed at a molar ratio of 9: 1, stirred, and dried by heating to obtain a crystalline sample. The sample was bluish brown.

Comparative Example 2 An aqueous solution of cuprous sulfate (cuprous sulfate heptahydrate: a special-grade reagent manufactured by Wako Pure Chemical Industries) and ferrous sulfate (ferrous sulfate heptahydrate: Wako Pure Chemical) An aqueous solution of an industrial company (special grade reagent) was mixed at a molar ratio of 9: 1, and the pH was adjusted to 7 with a 120 g / l aqueous sodium hydroxide solution, followed by heating and drying to obtain a crystalline sample. The sample was brown.

Comparative Example 3 An aqueous solution of cuprous sulfate (cuprous sulfate heptahydrate: a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) and ferrous sulfate (ferrous sulfate heptahydrate: Wako Pure Chemical Industries, Ltd.) An aqueous solution of an industrial company (special grade reagent) was mixed at a molar ratio of 9: 1, and the mixture was stirred and then filtered (toyo filter paper 5A1).
(10 mm standard) so as to have a metal content of 10%, and dried by heating to obtain a sample. The sample was brownish blue, hard and brittle.

Comparative Example 4 An aqueous solution of cuprous sulfate (cuprous sulfate heptahydrate: a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) and ferrous sulfate (ferrous sulfate heptahydrate: Wako Pure Chemical Industries, Ltd.) An aqueous solution of an industrial company (special grade reagent) was mixed at a molar ratio of 9: 1, and the mixture was stirred and then filtered (toyo filter paper 5A1).
(10 mm standard) so as to have a metal content of 10%, adjusted to pH 7 with a 120 g / l aqueous sodium hydroxide solution, and then dried by heating to obtain a sample. The sample was dark brown and hard.

Comparative Example 5 An excess amount of an aqueous tannic acid solution was added to an aqueous solution of ferrous sulfate (ferrous sulfate heptahydrate: a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was sufficiently stirred and 120 g / l. The pH was adjusted to 7 with sodium hydroxide to obtain an iron tannate suspension. Dissolved pulp (DP) having a dry weight of 8 kg and carboxymethyl cellulose having a dry weight of 2 kg are thoroughly disintegrated and mixed, and the above-mentioned iron tannate suspension is added thereto in an amount of 3 kg for a dry weight, followed by sufficient stirring, followed by papermaking and drying. I got The sample was black with no abnormalities on the surface and had no effect on the pulp as a carrier when dried. When the iron content of this sample was measured by the atomic absorption method, the iron content was 2.6%.

Test Example Deodorizing experiments were performed using the samples obtained in Examples 1 to 4 and Comparative Examples 1 to 5. The deodorization experiment was performed by enclosing 50 ppm of the target gas in a 1-l Erlenmeyer flask, charging the sample by 1.0 g by dry weight, and measuring the gas concentration 10 minutes and 30 minutes later. The target gas used was hydrogen sulfide, trimethylamine, and acetaldehyde, and the gas concentration was measured by a detector tube method. The test results are shown in Table 1. In the comparative example, a high deodorizing ability is exhibited depending on a target gas type, but a high deodorizing ability is not obtained for many gas types, and there is a concern about an influence on a carrier.

[0024]

[Table 1]

[0025]

As described above, according to the present invention, there is provided an inexpensive deodorant which exhibits excellent deodorizing ability against many malodorous gases, can be easily molded by any method, and is inexpensive. .

Claims (5)

[Claims] 1. A deodorant containing copper aminochlorotoluenesulfonate. 2. A deodorant composition comprising copper aminochlorotoluenesulfonate supported on a porous carrier. 3. A deodorant containing copper aminochlorotoluenesulfonate and ferrous tannate. 4. A deodorant composition in which copper aminochlorotoluenesulfonate and ferrous tannate are supported on a porous carrier. 5. The deodorant composition according to claim 2, wherein the porous carrier is pulp.