JPH01110365A - Deodorizer - Google Patents

Abstract

PURPOSE:To heighten a deodorizing effect, to lengthen a duration and to prevent secondary contamination, by using a complex composed of a specific polyamine or its derivative and a specific metal as an effective component. CONSTITUTION:A complex used as an effective component is composed of a polyamine or its derivative and a metal. The polyamine is shown in a formula (I): here, 1 is 2 or 3; m is any integer of 0-200; n is any integer of 1-200; R is hydrogen or an alkyl group which might be bonded to a polymer; and R' and R'' may be the same or different, and are hydrogen or -[(CH2)lNH]x-H (x is any integer of 0-100). The derivative of polyamine is a Schiff's base with salicylaldehyde or acetylacetone. The metal is Co, Fe, Ni, Cu, Mn, Ti, V, Ce or Mo.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a deodorant containing a complex of a polyamine and a metal as an active ingredient.

(Prior Art) In general, conventional methods for treating bad odors include adsorption methods using porous materials such as activated carbon and silica gel, absorption methods using water and surfactants, redox methods using oxidizing agents and reducing agents, etc.
Neutralization method with acid or alkali.

Biochemical methods using microorganisms and enzyme preparations, other combustion methods,
Various methods such as masking methods are known, but all of them have many drawbacks such as low deodorizing effect, short duration of deodorizing effect, secondary contamination, and high cost.

(Problems to be solved by the present invention) The present invention has a high deodorizing effect and a long duration.

The object of the present invention is to provide a deodorizing agent that does not cause secondary contamination and can be manufactured easily on an industrial scale.

(Means for Solving the Problems) The present inventors have previously discovered that metal complexes of Schiff bases have a strong deodorizing effect, but furthermore, metal complexes with other compounds other than Schiff bases have a strong deodorizing effect. It was also predicted that it has deodorizing ability.

Based on this knowledge, we screened many compounds, and as a result, we discovered that metal complexes of polyamines have extremely strong deodorizing ability, and completed the present invention.

The gold mta form of the polyamine which is the active ingredient of the present invention has the formula [
I] and Co, Fs, Ni,
It consists of one or more metals selected from Cu-Mn, Ti, V, Ce, and metal.

“p (In the formula, Q is 2 or 3, m is any integer from O to 200, n represents any integer from 1 to 200.

R represents hydrogen or an alkyl group which may be bonded to a polymer, and R' and R' may be the same or different and represent hydrogen or -((C
HI), NH) ing. In addition, chelate resins in which polyamines are introduced as coordinating groups in place of the exchange groups of ion exchange resins are used for selective adsorption of heavy metals, taking advantage of their excellent ability to form complexes.

However, there are no reports that these metal complexes have deodorizing ability, and the use of these metal complexes as deodorants is a completely new finding.

Typical components that cause bad odors are ammonia, hydrogen sulfide, mercaptans, and amines. Among them, hydrogen sulfide and mercaptan have an extremely low olfactory threshold, and even a very small amount can give off a strong bad odor, so they cannot be used in conventional deodorants. It is a source of bad odors that is difficult to remove.

The deodorizing agent of the present invention has a particularly effective deodorizing ability against these sources of bad odors that have conventionally been considered difficult to remove.

The deodorizing mechanism is currently unknown, but it works very quickly against hydrogen sulfide and mercaptan odors.

In addition, its ability is effectively exhibited in both dry and wet conditions, so it can be used in a wide range of applications without being restricted by the environment in which it is used.

The polyamine used in the present invention may be a low-molecular-weight polyamine such as ethylenediamine or diethylenetriamine, but high-molecular-weight polyamines such as polyethyleneimine are more preferable for formulation as a deodorant, for example, those that form a complex with polyethyleneimine. Silica gel is produced by reacting metal salts in an aqueous solvent to form a complex.

A bulk deodorant powder can be easily obtained by holding the deodorant in an appropriate manner such as impregnating or coating it on activated carbon, fibers, polymers, nonwoven fabrics, or other substrates depending on the purpose.

It is also suitable to use a polyamine that has been bonded to the polymer in advance. Commercially available chelate resins are available as such polyamines.

For example, a polymer having a benzene ring can be chloromethylated and then dechlorinated to obtain a polymer to which any polyamine is bound. In order to make the polyamine bound to these polymers into a complex with a metal, the polymer is dispersed in water, an organic solvent, or a mixed solvent thereof,
All you have to do is react the metal salt in it.

Metals that form complexes are generally used in the reaction in the form of salts, such as Cf1-, SO2''-1NO, -1CH,
Salts such as COO- are preferred.

It is also good to add hydroxides of alkali metals or alkaline earth metals as appropriate to remove liberated acid radicals and adjust the pH of the reaction system.

As described above, all of the active ingredients of the present invention can be easily synthesized industrially using commercially available materials as raw materials.

The powder of the deodorant made of the metal complex of polyamine thus obtained is used as a deodorant by blending with other ingredients, molding it, or putting it into a container as it is, depending on the purpose.

Next, the present invention will be described in more detail with reference to Examples.

Example 1 Styrene-divinylbenzene copolymer beads 12.6
g was chloromethylated with chloromethyl methyl ether using anhydrous tin (IV) chloride as a catalyst. To this was added 65.1 g of Schipf base obtained from salicylaldehyde and diethylenetriamine, and by dehydrochlorination, the Rischiff base was bound to the beads via the secondary amine derived from diethylenetriamine. This was treated in 6N hydrochloric acid at 60°C for 24 hours to decompose the Schiff base and obtain beads to which only diethylenetriamine was bound.

10 g of the obtained beads were dispersed in dimethylformamide, and 5.0 g of cobalt acetate tetrahydrate was added and reacted to obtain 12.2 g of beads bound to the complex.

Put 0.5g of these beads into a Tetra Vac, and
0 ppm of ethyl mercaptan 3Q was sealed.

The concentration of ethyl mercaptan was measured using a gas detection tube at predetermined intervals to determine the deodorization rate.

A very strong deodorizing effect was observed. The results are shown in Table 1.

Example 2 0 of the cobalt complex-bound beads obtained in Example 1
．． 5 g was put into a Tetra Pak, and 1800 ppm of hydrogen sulfide 2Q was sealed. When the concentration of hydrogen sulfide was measured at predetermined intervals using a gas detection tube and the deodorization rate was determined, a very strong deodorization effect was observed. The results are shown in Table 2.

Example 3 Commercially available chelate resin (product name: Diaion CR-20
) Log was dispersed in dimethylformamide, and 5.0 g of cobalt acetate tetrahydrate was added and reacted to obtain 11.5 g of a resin in which a complex was formed. 0.5 g of this resin was put into a Tetra Vac, and 240 ppm of ethyl mercaptan 3Q was sealed therein. When the concentration of ethyl mercaptan was measured at predetermined intervals using a gas detection tube to determine the deodorizing rate, it was found that the product had a very strong deodorizing effect. The results are shown in Table 1.

Example 4 0.5 g of the cobalt-bonded chelate resin obtained in Example 3 was put into a Tetra Vac, and 1800 ppm was added.
of hydrogen sulfide 2a was sealed. When the concentration of hydrogen sulfide was measured at predetermined intervals using a gas detection tube to determine the deodorization rate, a very strong deodorization effect was observed. The results are shown in Table 2.

Example 5 The diethylenetriamine-bonded beads TOG obtained in Example 1 were dispersed in a mixed solvent of dimethylformamide and water, 6.0 g of ferrous chloride was added, and an aqueous sodium hexahydroxide solution was added to the mixture under almost neutral conditions. 10.6 g of complex-bound beads were obtained. 0.5 g of these beads were placed in a Tetra Vac, and 240 ppn+ of ethyl mercaptan 3Q was sealed therein. When the concentration of ethyl mercaptan was measured at predetermined intervals using a gas detection tube and the deodorization rate was determined, a very strong deodorization ability was observed. The results are shown in Table 1.

Example 6 2.3 g of polyethyleneimine having a molecular weight of 750 was dissolved in water, and 1.7 g of cobalt acetate tetrahydrate was added and reacted. 10 g of silica gel powder was added to this aqueous solution and concentrated to dryness to obtain a silica gel powder in which the polyethyleneimine-cobalt complex was retained. 0.5 g of this was taken and put into a Tetra Vac, and 1800 ppm of hydrogen sulfide 2Q was sealed therein. When the concentration of hydrogen sulfide was measured at predetermined intervals using a gas detection tube and the deodorization rate was determined, it was found that the product had a very strong deodorization ability.

The results are shown in Table 2.

Example 7 0 of the cobalt complex-bound beads obtained in Example 1
．． 5 g was dispersed in 50 wrQ of water and poured into an air washing bottle.

240 ppm ethyl mercaptan 3Q sealed in a Tetra-Pak was circulated through the air wash bottle by an air pump. When the concentration of ethyl mercaptan was measured using a detection tube after 3 hours, no ethyl mercaptan was detected, indicating that it had a very strong deodorizing ability even in water.

Table 1 Deodorizing effect on ethyl mercaptan Table 2 Deodorizing effect on hydrogen sulfide Agent Patent attorney Door 1) Parent Male procedural amendment November 6, 1988

Claims (3)

[Claims] (1) A deodorant whose active ingredient is a complex consisting of a polyamine and a metal. (2) The deodorant according to claim 1, wherein the polyamine is a compound represented by formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, l is 2 or 3, m is any integer from 0 to 200, n is any integer from 1 to 200, and R is hydrogen. or represents an alkyl group that may be bonded to a polymer, and R' and R'' may be the same or different and represent hydrogen or -[(C
H_2)_lNH]_x-H (where x is from 0 to 10
(represents any integer up to 0)) (3) Metal is Co, Fe, Ni, Cu, Mn, Ti, V
, Ce, or Mo.