JPS621752A - High polymer material having deodorizing function - Google Patents

Abstract

PURPOSE:The titled material, obtained by linking a metallophthalocyanine containing hydrophobic bonds to a hydrophobic high polymer through hydrophobic bonds and capable of decomposing water-soluble and water-insoluble materials giving out offensive smell simultaneously in a short time and lasting semipermanently the deodorizing effect. CONSTITUTION:A high polymer material obtained by linking hydrophobic groups (R) of a metallophthalocyanine having the structure expressed by the formula and groups (-X) with hydrophobic groups to a hydrophobic high polymer, e.g. polystyrene, through hydrophobic bonds and supporting 0.5-20wt% above- mentioned metallophthalocyanine. Preferably, the above-mentioned metallophthalocyanine has Fe atom as the central metal atom (M), and specifically iron octyl phthalocyaninetetracarboxylate having long-chain alkyl groups as the hydrophobic groups (R), etc., is preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polymeric substance having a deodorizing function of converting a substance emitting a foreign odor into a substance with a burning odor.

[Conventional technology]

Conventional methods for deodorizing bad odors include activated carbon adsorption, catalytic combustion, oxidation using ozone or chemicals,
Neutralization methods, bacterial decomposition methods, and enzyme decomposition methods are known, but all of them have shortcomings such as short-lasting deodorizing ability, low deodorizing efficiency, and secondary contamination. .

Malodorous substances in daily life include ammonia,
Amines, hydrogen sulfide, mercaptans.

These include indole and carbonyl compounds. These substances are decomposed by the action of biological enzymes as oxidation catalysts, as described in JP-A-55-32519.

Among biological enzymes, metalloporphyrins and metalvolfrazins are excellent, and they are advantageous in that they can be synthesized artificially and are relatively easily available, as disclosed in JP-A-50-54590, for example. It is.

The invention of using metal porphyrins and metal volfrazines as a deodorant can be seen in the invention of the present inventors.
This is already known from the above-mentioned Japanese Unexamined Patent Publication No. 55-32519. The disclosed deodorant is superior to other deodorants.

[Problem that the invention seeks to solve]

This invention was made as a result of further research,
Utilizing the deodorant disclosed in the above-mentioned publication, we have developed a highly deodorizing deodorant that can decompose water-soluble and water-insoluble off-odor substances simultaneously and in a short time, and is a type of deodorant that has been improved in terms of practicality. The aim is to provide molecular substances.

[Means for solving problems]

The present inventor obtained the following findings through research on the use of metal porphyrins and metal volfrazines as deodorants.

In order for a deodorant to act as an oxidation catalyst on all kinds of odor substances and decompose them in a short period of time, it is necessary to have the following functions: ■ Function as oxidase, ■ Function as peroxidase, and ■ Function as oxygenase. . It is believed that enzymes do not perform these three functions simultaneously in vivo.

Among the metal porphyrins and the metal volfrazines, the metal phthalocyanine shown in the structural formula of FIG. 1 is excellent as a deodorant because it has the possibility of simultaneously exhibiting the above-mentioned functions (1) to (3). However, it is difficult to obtain an even better deodorant using metal phthalocyanine alone. If -X in the above structural formula is a group with a small steric structure, it is shown in Figure 3 (
The metal phthalocyanine dimer shown in a) or the same figure (
Metal phthalocyanine-p-oxodimer shown in b) is produced, which weakens the catalytic activity. Therefore, it is necessary to prevent dimers from being generated. According to the results of various experiments, metal phthalocyanine hydrophobically binds to proteins, which are polymeric substances, in vivo, and maintains its activity as an oxidation catalyst.

Based on the above knowledge, the present invention prevents the formation of such dimers by hydrophobically bonding metal phthalocyanine into a polymer and causing steric hindrance between the metal phthalocyanines by the polymer chain. .

However, even if metal phthalocyanine is bound to a polymeric substance, if the amount of metal phthalocyanine bound is too large, the probability of close contact between metal phthalocyanines increases and dimers are formed, which may actually worsen deodorizing efficiency. . On the other hand, if the amount of metal phthalocyanine is too small, the deodorizing effect cannot be maintained. According to the results of various experiments, the appropriate amount of metal phthalocyanine is 0.5 to 20% by weight based on the overall view. More preferably, it is 1.0 to 10% by weight.

As shown in Figure 2, in order to bond metal phthalocyanine to a polymer, at least one - A hydrophobic group (indicated by R in the figure) is introduced to form a hydrophobic bond.

As the polymer, for example, polyolefin-based, vinyl-based, polyester-based, acrylic-based, polyamide-based, polypeptide-based, polyurethane-based, polycarbonate-based, polyether-based, or diene-based polymers can be used. It may have a three-dimensional structure, it may be a natural polymer substance or a synthetic polymer substance, it may be a substance without functional groups like polyolefins, but it does not have a hydrophobic part like polyvinyl alcohol or polyacrylic acid, Polymers with only wood-loving parts are not preferred.

The hydrophobic group R of the metal phthalocyanine is, for example, a long-chain alkyl group, which is bonded to the metal phthalocyanine to form an ester or amide.

The central metal M of the metal phthalocyanine is, for example, Fe, Go.
, Mn, Ti, V, Ni, Cu, Zn%No, W, O
s can be used. Preferably, it is Fe or Go, or a mixture of Fe and CO. The -X group of the metal phthalocyanine other than the functional group for hydrophobic bonding may be any arbitrary group, such as a hydrogen group, a lower alkyl group, a substituted alkyl group (for example, a chloromethyl group), a halogen group, or an alkyl silicon group.

[Effect]

As mentioned above, metal phthalocyanine is bound (
(see Figure 2), the metal phthalocyanines are hindered by the polymer chains, resulting in steric hindrance, making it difficult to form dimers (see Figure 3). In the same way that metal phthalocyanine maintains its catalytic activity in vivo through hydrophobic bonds, metal phthalocyanine is supported on polymeric substances through hydrophobic bonds, so it can fully demonstrate its function as an oxidation catalyst. . By introducing appropriate groups into a polymeric substance, a parent region and a hydrophobic region can be created. Therefore, water-soluble off-odor substances tend to infiltrate into the former region, and water-insoluble off-odor substances easily enter into the latter region, so both water-soluble and water-insoluble off-odor substances can be absorbed simultaneously and in a short period of time. It can be resolved in time.

The metal phthalocyanine in the polymeric substance has the three functions (1) to (3) mentioned above for water-soluble or water-insoluble off-flavor substances, and has the following actions to decompose the off-odor substances.

■ Action as oxidase Oxidation reaction by molecular oxygen (autooxidation effect by oxygen in the air).

2(Sub)H+ 02 Po1-MPc 5ub
-Sub+ H2O2 umbrella Sub during the ceremony is 5ubst
Abbreviation for rate (substrate).

Po1-MPc: Polymer substance to which metal phthalocyanine is bound (Sub) H: Off-odor substance such as H2S, R-9)I
(mercaptan derivative), R-CHO (aldehyde derivative), R-Nl2 (amino derivative), R-OH
(Alcohol derivative) Sub-Sub: Oxidation product ■ Action as peroxidase Oxidation reaction by hydrogen peroxide (marked 1) produced in ■ above (
■It occurs in a chain reaction to -).

2(Sub)H+ H2O2−−−→5ub−9ub
+2H20 ■ Action as oxygenase For example, reaction to oxidize and cleave a malodorous substance consisting of a heterocyclic compound with an indole nucleus or a pyridine nucleus. In the case of an indole nucleus, the following reaction occurs.

The products resulting from oxidative cleavage may be further decomposed by the reactions (1) and (2) above.

〔Effect of the invention〕

The polymeric substance of the present invention can decompose almost all malodorous substances, whether water-soluble or water-insoluble, that are present in the daily life of humans through the reactions described in (1) to (4) above.

Furthermore, the substance itself does not absorb or store off-flavor substances, nor is it consumed in the deodorizing reaction system, and the metal phthalocyanine is not bound as a component of the polymer chain. This prevents it from falling off due to aging or cleaning. Therefore, the deodorizing effect can be maintained semi-permanently.

Since it is a polymeric substance, it can be in the form of fibers, films, chips, rubber, powders, or objects by itself, copolymerized with other polymeric substances, or blended with other polymeric substances. Can be formed into structures. It can also be mixed into paper. It can also be mixed into paints and the like. Therefore, depending on the respective shape, for example clothing, bedding, carpets.

It can be used in all kinds of polymer materials currently used, such as building materials, filters for air purifiers and sewage treatment equipment, packaging materials, and containers, and can be given a deodorizing function.

〔Example〕

Example 1. When a small amount of hydrochloric acid is added to an aqueous solution of iron phthalocyanine tetracarboxylic acid and octyl alcohol is added little by little while stirring vigorously, iron phthalocyanine tetracarboxylic acid octyl ester will float. This floating material is extracted and purified with benzene to obtain a benzene solution of iron phthalocyanine tetracarboxylic acid octyl ester. After adjusting the concentration of iron phthalocyanine tetracarboxylic acid octyl ester to 1.0% by weight, polystyrene was
Dissolve in weight%. When the benzene is then evaporated, a substance having a structure shown in FIG. 2 in which iron phthalocyanine tetracarboxylic acid octyl ester is hydrophobically bonded and supported on polystyrene in an amount of 10% by weight is obtained.

Example 2. When a small amount of hydrochloric acid is added to an aqueous solution of cobalt phthalocyanine octaol, kept at 90°C, and pelargonic acid is added little by little while stirring vigorously, cobalt phthalocyanine octyl pelargonic acid ester floats. This suspended substance is extracted and purified with chloroform to obtain a chloroform solution of cobalt phthalocyanine octylpelargonic acid ester. After adjusting the concentration of cobalt phthalocyanine octyl pelargonic acid ester to 0.5% by weight, polyacrylonitrile is dissolved to a concentration of 10% by weight. Thereafter, when chloroform is evaporated, a material in which 5% by weight of cobalt phthalocyanine octyl pelargonic acid ester is hydrophobically bonded and supported on polyacrylonitrile is obtained.

Example 3. When laurylamine is added to a benzene solution of iron phthalocyanine tetracarbonyl chloride, iron phthalocyanine tetracarbonyl lauryl amide is obtained.

The purified benzene solution is adjusted to have a concentration of iron phthalocyanine tetracarbonyl lauryl amide of 1.0% by weight, and then the polyester resin is dissolved therein so as to have a concentration of 10% by weight.

When benzene is then evaporated, a material in which 10% by weight of iron phthalocyanine tetracarbonyl laurylamide is hydrophobically bonded and supported on the polyester is obtained.

The polymer substances obtained in Examples 1 to 3 above were packed in a glass tube, and vapors such as ammonia, amines, hydrogen sulfide, and mercaptans were passed through the tubes, and the gas chromatograph examination revealed that these substances were well decomposed. It was shown that

Performance did not deteriorate at all even after one year of continuous testing. Furthermore, it has received very good reviews for natural foul-smelling substances such as manure, fish pulp, and sewage sludge. In addition to the above-mentioned gas chromat gelaf, we also conducted a sensitivity test using a monitor during the evaluation, and the product also received better evaluations than conventional deodorants.

[Brief explanation of the drawing]

Figure 1 shows the structural formula of metal phthalocyanine, Figure 2 shows an example of a structure in which metal phthalocyanine is bonded to a polymer, and Figure 3 (a) and (b) show a dimer of metal phthalocyanine. FIG. Patent applicant Earthclean Co., Ltd. Figure 1

Claims (1)

[Claims] Structural formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ At least one of the -X groups of the metal phthalocyanine has a hydrophobic group, and the hydrophobic group of the metal phthalocyanine is hydrophobic in a hydrophobic polymer. A polymer substance having deodorizing function, characterized in that 0.5 to 20% by weight of the metal phthalocyanine is bonded to the polymer and supported on the polymer.