JPH01320061A - Compound for deodorizing - Google Patents

Abstract

PURPOSE:To allow the effect to last for a long period of time by including porphyrin metal complex and a metal salt and/or metal simple substance. CONSTITUTION:A porphyrin metal complex signifies a general name of chemical substances presented by Eq. I (where X is H of at least one substituent and unsubstituent, and M a metal or metal ion having oxidative/reductive property). Metal to form the metal salt and/or metal simple substance shall for ex. be Cu, Co, Zn, Ni, Ag, while examples of the salt of the metal salt be acetate, sulfate, nitrate, chloride, and carbonate, preferably being the first named two. The deodorizing compound according to existing invention shall preferably contain a metal salt and/or metal simple substance in 10-1,000 parts by weight to the porphyrin metal complex in 100 parts by weight.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is mainly directed to the invention. The present invention relates to a novel deodorizer and composition that maintains a high degree of deodorizing ability for a long period of time and is used in dJ desks, refrigerators, air conditioners, etc.

[Conventional technology]

Conventional methods for deodorizing bad odors include activated carbon adsorption, catalytic combustion, ozone or chemical oxidation, neutralization, bacterial decomposition, and enzymatic methods, but all of them have high running costs. It has many drawbacks, such as being expensive, difficult to manage, lacking in sustainability, and having relatively low deodorizing efficiency.

In particular, among these common deodorizing treatment methods, the method of decomposing the oxidative gas using an oxidizing agent is the most effective, but generally potassium dichromate, jinrenjiang, etc. are used as the agent. However, this treatment method is not recommended for single-ship use because it requires careful handling, there is a risk of secondary contamination due to the cross-reagent, and the reaction temperature is high.

As a result of research into deodorants that do not have the above-mentioned drawbacks and exhibit excellent effects, the present inventors discovered that
In 355, it was discovered that porphyrin metal complexes and porphyrazine metal complexes, which are metal complexes with redox ability, have excellent deodorizing performance. It has been found that particularly excellent deodorizing performance can be obtained by combining it with

However, for long periods of time, such as in cars, refrigerators, and air conditioners,
In fields where a high degree of anti-inflammatory performance is required, the former porphyrin gold 18+m complex and porphyrazine metal complex showed much superior deodorizing performance than the previous %ya deodorant, but they did not last for a long time. It is clear that there is much need for further improvement and consideration in maintaining the anti-inflammatory ability of the skin.

[Problem to be solved by the invention]

The object of the present invention is to provide a novel deodorant composition that fundamentally solves the above-mentioned improvements over the prior art, that is, it is characterized by containing a porphyrin metal complex and a metal salt or/and an elemental metal. The object of the present invention is to provide a novel deodorant composition that does the following.

From the present invention, the characteristics of conventionally known porphyrin metal complexes and porphyrazine metal complexes, namely, rapid decomposition rate of malodor, high decomposition rate, and usability in a wide range of temperature conditions from low to high temperatures. In addition to being widely usable in both gas and aqueous phases, the present invention provides an innovative deodorant that maintains its effects over a long period of time.

[Means for solving problems]

The present invention was made in order to solve the above-mentioned problems, and provides a novel deodorant composition comprising a porphyrin gold t4 complex and a metal salt or/and an elemental metal. This is what we provide.

In the present invention, "porphyrin" is a general term for compounds obtained by replacing surrounding hydrogen atoms with a basic skeleton of porphine, which is a broken compound consisting of four pyrrole groups bonded with methylene groups. More specifically, it is described in "Chemistry of Porphyrins", pages 2 to 5, April 1, 1981, edited by Tetsube Hiranaga, published by Kyoritsu Publishing Co., Ltd., first edition, first printing, Kyoritsu Chemical Library [phase]. It is a chemical substance. Also,"
"Porphyrin gold 248 bodies" refers to the following formula x X
is a general term for chemical properties represented by the following formula (wherein Y is at least 1 represents a substituent group and an unsubstituted group H, and M represents a metal or metal ion having redox properties.

As the porphyrin metal complex or porphyrazine gold part complex used in the present invention, porphyrin gold J! @i body,
There are monoaza, diaza, triaza, tetraaza-porphyrin complexes, phthalocyanine gold jA complexes, etc. Among them, it is preferable to use phthalocyanine metal complexes from the viewpoint of ease of production, deodorizing effect, economic effect, etc. .

The metals serving as the metal ions represented by M in the basic skeleton include sodium, potassium, calcium, barium,
These include tin, chromium, iron, cobalt, nickel, manganese, osminium, titanium, beryllium, molybdenum, and tungsten, among which iron, cobalt, manganese, nickel, and zinc are preferred.

Examples of the substituents used in the present invention include alkyl groups, substituted alkyl groups, halogen groups, nitro groups, ami7 groups, azo groups,
Thiocyanate group, carboxyl group, carbonyl chloride group, carboxylamide group, nitrile group, hydroxyl group, alkoxyl group, phenoxydyl group, sulfonic acid group, sulfonyl chloride group, sulfonamide group, thiol group, chloromethyl group, alkyl silicon group, vinyl group In addition to these, there are also alkali salts of carboxyl groups and sulfonic acid groups.
Of these, one or two or more are used, but among them, carboxyl groups, sulfonic acid groups, alkali salts thereof, amino groups, halogen groups, hydroxyl groups, etc. are used, and particularly preferred are carboxyl groups, sulfonic acid groups, or hydroxyl groups. These alkali salts and amino groups are used, and grains are preferably carboxyl groups or salts thereof or amino groups. More preferred are polycarboxylic acids, especially tetracarboxylic acids, octacarboxylic acids, or mixtures thereof.

(9) Examples of the metal of the "metal salt or/and elemental metal" in the present invention include copper, cobalt, zinc, nickel, and silver, with steel and cobalt being particularly preferred; examples of the metal salt include, for example. Examples include acetates, sulfates, nitrates, chlorides, carbonates, etc., and acetates and chloride salts are preferred.

The deodorizing composition of the present application preferably contains 100 parts by weight of the porphyrin metal complex and 114 parts of gold 114 salt or/and an elemental metal.
It is preferably contained in an amount of 0 to 1000 parts by weight, particularly preferably 30 to 500 parts by weight, and most preferably 60 to 300 parts by weight.

The method of using the deodorant in the present invention is not particularly limited, but porphyrins may be dissolved or dispersed in a specific aqueous solution or organic liquid, or activated carbon, kudzu kudzu, zeolite, etc. that have adsorption capacity may be used. It is used by being adsorbed onto solid objects, or attached or chemically bonded to pumice, foamed concrete, various ceramics, various fibers, leather, rubber, plastics, paper, pulp, etc.

Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples in any way.

Examples 1-3 Iron phthalocyanine octacarboxylic acid was dissolved in a 5% caustic soda solution to obtain an approximately 3% concentration iron phthalocyanine octacarboxylic acid bath solution.

In this solution, "silica honeycomb (thickness 10 m1111
Honeycomb-like silica with a cross-sectional wavy through-hole with a diameter of 20 pieces and a cell count of about 300 cells/square inch) After being immersed and supported, it was soaked in vinegar and then soaked in a 5-chip water bath of E11 steel (CuCs). The support of Example 1 was obtained by immersion support.

By the same method, [zinc acetate (ZnACa), "
The supports of Example 2.3 were obtained using 5% water bath liquid gold of each of Cobalt acetate (Cobalt and Ca).

Examples 4 and 5 "Iron phthalocyanine octacarboxylic acid" was dissolved in a 5% caustic soda solution to obtain an "iron phthalocyanine octacarboxylic acid solution" of about 11(1)1 degree. In this solution, natural zeolite granules (Nitto Funka Kogyo KKfi, Zo
, No. 5, size 4 to 6)" was then dipped and supported in a "5% water bath solution of copper acetate (CuAca)" to obtain the support of Example 4.

A support of Example 5 was obtained by a four-ball method using a "cobalt phthalocyanine octacarboxylic acid bath solution" instead of an "iron phthalocyanine octacarboxylic acid bath solution."

Example 6 Implementation? lJ 1 to 2, except that the concentration rL of the "iron phthalocyanine octacarvone fRm solution" used was set to 4 and that "5% aqueous solution of Cu5Oa" was used instead of "5% aqueous bath solution of CuAca". The support of Example 6 was obtained in the same manner as in Example 1.

Example 7 The concentration of the “iron phthalocyanine octacarvone #1. solution” used in Example 4 was set to 2%, and the “Cu
5% water bath solution of Ac 2” instead of “Cu 804
All procedures were carried out in the same manner as in Example 4, except for using a 4-ti aqueous solution of A carrier of IJ7 was obtained.

Example 8 The concentration of "iron phthalocyanine octacarvone@#*J" used in Example 1 was 4%, and "5% of copper acetate was used.
A support of Example 8 was obtained in the same manner as in Example 1, except that ``copper'' was used instead of ``water bath liquid''.

Comparative Example 1 A support t- of Comparative Example 1 was obtained by the same method as in Example 1 except for "acetic acid steel" in Example 1.

Comparative Example 2 A support of Comparative Example 2 was obtained in the same manner as in Example 1 except that "iron phthalocyanine octacarboxylic acid" was removed.

The deodorizing effect of each of the deodorizing carriers obtained in Examples 1 to 8 and Comparative Examples 1 to 2 above was evaluated by Hisa's deodorizing rate measuring method.

The results are listed in Table 1@1.

In addition, the mixing ratio of the porphyrin gold maple inscription and the metal salt or/and the metal used in the Examples and Comparative Examples is shown in Table 2.

[Deodorization rate measurement method]

Figure 1 - Measurements were taken using the measuring device shown.

The foul-smelling gas flows from the container 1 containing the foul-smelling gas in the direction of the arrow at a desired flow rate through the flowmeter 2, and -
After mixing the air flowing in the direction of the arrow through the flow meter 4 with the air flowing in the direction of the arrow at a desired flow rate using the air pump 3 using the mixer 5, the deodorizing carrier 7 obtained in this example was stored. It passes through the deodorizing carrier holder 8 and is exhausted from the exhaust section 10.

Methyl mercaptan and hydrogen chloride were used as malodorous gases in the measurement of the deodorizing carrier of this example, and each gas was mixed with air, and the gas modification was 2p.
The measurement temperature was set at 20°C, and the gas flow rate was adjusted to 0.1rrL/
After the predetermined concentration and flow rate are constant, the deodorization rate after the elapse of time is determined, and 1,000
Table 1 shows the deodorization rate after the elapse of time.

In addition, the above deodorization rate was determined by sampling at the same time at the downstream sampling port 6 and the secondary sampling port 9, and measuring the downstream gas concentration and the secondary gas, 2# degree, respectively.
The percentage of the concentration difference between the two gases with respect to the above-mentioned downstream gas concentration was defined as the ff4 beauty ratio.

The concentration was measured using a Kita type detection tube.

Table 1 Table 2 [Effects of the Invention] The deodorizing composition of the present invention is mainly used in automobiles, refrigerators, air conditioners, etc., and has a high degree of deodorization for a long period of time. : Used as a deodorant that retains its properties.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of the deodorization rate measuring device used in Examples and Comparative Examples. 1...Standard gas 2...Flowmeter 3...Air feed pump 4...Flow rate needle 5 ......Standard gas and air mixer 6...
......-Next side sampling port 7...
...Deodorizing carrier 8...Deodorizing carrier holder 9...
...Secondary side sampling port 10...
・Exhaust part

Claims (9)

[Claims] (1) A deodorizing composition containing a porphyrin metal complex and a metal salt or/and an elemental metal. (2) The porphyrin metal complex is a porphyrin metal complex of the following formula (a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X represents at least one substituent and unsubstituted H] Claim 1
The deodorizing composition described in Section 1. (3) The porphyrazine metal complex is a porphyrazine metal complex of the following formula (b) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Y represents at least one substituent and unsubstituted H] A deodorizing composition according to claim 1. (4) The deodorizing composition according to claim 3, wherein the porphyrazine metal complex is a phthalocyanine mono- or polycarboxylic acid metal complex. (5) The deodorizing composition according to claim 3, wherein the porphyrazine metal complex is a phthalocyanine mono- or polyamine metal complex. (6) The deodorizing composition according to claim 4, wherein the metal of the phthalocyanine mono- or polycarboxylic acid metal complex is iron or cobalt. (7) The deodorizing composition according to claim 4, wherein the phthalocyanine polycarboxylic acid metal complex is octacarboxylic acid. (8) The deodorizing composition according to claim 1, wherein the metal salt and/or the metal element is copper, cobalt, or zinc. (9) The deodorizing composition according to claim 1, wherein the metal salt is an acetate, a sulfate, a nitrate, or a chloride.