JPH07114914B2 - Deodorant material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a deodorant material. More specifically, it relates to a deodorant material containing a carboxyphthalocyanine metal complex as a deodorant component.

[Prior Art] As a method of eliminating various odors including a bad odor, sensory deodorization, chemical deodorization, physical / chemical deodorization, physical adsorption deodorization,
Methods such as biological deodorization are used.

Currently, activated carbon is the most commonly used deodorant for malodors, but the action of activated carbon is physical adsorption and deodorization, and therefore, not only the effect decreases when the adsorption reaches the saturation point, It has drawbacks such as almost no adsorption capacity for ammonia.

[Problems to be solved by the invention]

Most of the major malodorous substances have mobile hydrogen, and it is thought that deodorization is possible by dehydrogenating and oxidizing this, and dimerizing, water-solubilizing, and making it non-volatile, and in vivo enzymes act on malodorous substances. You can see some examples. Enzymes that perform these reactions include hematoporphyrin, which binds to the apoprotein, turns iron into a trivalent spin electronic state, and the histidine-imidazole nitrogen of the protein coordinates to the fifth coordination site. A carboxyphthalocyanine metal complex having catalytic activity similar to this, for example, an octacarboxyphthalocyanine iron complex, decomposes by a reaction mechanism similar to that of catalase and exhibits a relatively high specific activity of about 6 times that of hemin.

By the way, the deodorizing effect of such a carboxyphthalocyanine metal complex has been found by the present inventors to be effective not only in ammonia but also in removing malodors such as hydrogen sulfide. For ease of handling, it was considered to be adsorbed on granules and styrene-divinylbenzene copolymer microporous beads were selected here as granules.

Further, since the deodorizing effect of the carboxyphthalocyanine metal complex is sufficiently exerted in the presence of water, it is preferable that the microporous beads are also used while retaining water therein. In order to suppress evaporation of water, a water-absorbing substance is used together with it.

[Means for solving problems]

Therefore, the present invention relates to a deodorant material, which comprises a styrene-divinylbenzene copolymer microporous bead holding an aqueous solution of a carboxyphthalocyanine metal complex or a water-absorbing substance.

The carboxyphthalocyanine metal complex is represented by the following formula: 4,4 ′, 4 ″, 4-tetracarboxyphthalocyanine-metal complex Alternatively, a complex of trivalent iron, cobalt, nickel, copper or the like such as 4,5,4 ′, 5 ′, 4 ″, 5 ″, 4,5-octacarboxyphthalocyanine-metal complex is generally used.

The carboxyphthalocyanine metal complex can also be used in the form of a complex with a compound or oligomer having a hydroxyl group, an amino group, an epoxy group, a polydinium group and the like having reactivity with a carboxyl group. In this case, the molecular dispersibility of the carboxyphthalocyanine metal complex is improved, and the metal carboxyphthalocyanine metal complex is more easily retained on the microporous beads.

An aqueous solution of these carboxyphthalocyanine metal complexes is preferably used together with a water absorbing substance. As the water-absorbing substance, glycerin, ethylene glycol, polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polyvinylpyrrolidone, starch and the like are used.

Styrene-vinylbenzene copolymer microporous beads that hold each of these substances is a resin in which the divinylbenzene moiety acts as a cross-linking point of the styrene substrate and has a pore size of 16 to 1800Å and a pore size of 0.1 ml / g or more. It has a volume and is commercially available as the Mitsubishi Kasei Kogyo product Diaion HP series.

For holding the metal complex on the microporous beads, for example, in the case of carboxoxyphthalocyanine iron, it is prepared by a solution thereof, and the means such as dipping and spraying with the solution is used.
This solution is prepared and used, for example, as a solution dissolved with an equivalent amount of potassium hydroxide.

In the actual treatment such as dipping, the above metal complex solution to which ethanol or the like is added for smoother impregnation is used, and when a water-absorbing substance is used, it is added at the same time as ethanol or the like. It After soaking, heat to about 40-150 ℃ to evaporate ethanol, and add water that was evaporated together with it. Add a small amount of potassium hydroxide in addition to the metal complex, or about 1 to the amount of beads. A solution having a composition containing 100% by weight of a water-absorbing substance is impregnated to about 20 g per 100 g of microporous beads.

[Operation] and [Effects of the Invention] Since the deodorant material according to the present invention is granular, it can be housed in an arbitrary container and used, and therefore convenience in handling is recognized.

Further, the carboxyphthalocyanine metal complex effectively acts on the malodor decomposition of substances having mobile hydrogen such as ammonia and hydrogen sulfide, but its deodorizing effect is greatly affected by the amount of water when it acts.

In the present invention, by holding the carboxyphthalocyanine metal complex, which is greatly affected by the amount of water, in the styrene-divinylbenzene copolymer microporous beads having a large amount of water, the deodorizing ability that it originally has is sufficient. Deodorant materials that can be used for
This deodorant material can effectively deodorize malodorous substances such as ammonia and hydrogen sulfide, but the effect is more remarkable when a water absorbing substance is used together.

〔Example〕

 Next, the present invention will be described with reference to examples.

Example 1 5 g of octacarboxyphthalocyanine iron complex was added to an aqueous solution in which an equivalent amount of potassium hydroxide was dissolved to prepare a solution having a total volume of 100 ml.

100 g of styrene-divinylbenzene microporous beads (Diaion HP-20 manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) was immersed in a solution prepared by adding 15 g of ethanol to the above complex solution, then pulled up, and heated at 100 ° C. for 3 hours to produce ethanol. Was evaporated. Measured from the weight difference, supplemented with water that seems to have evaporated together with ethanol, a solution of 20 g (composition: complex 4.4 g% by weight, potassium hydroxide 2.1% by weight, water 93.
5% by weight) was impregnated into the microporous beads.

In this way, 1 g of microporous beads in which the iron complex was dipped and held was adjusted to a humidity of 65% and filled with air.
The sample was placed in a 5 liter Teflon bag made of Teflon and set as shown in FIG. 1 to measure the deodorizing effect.

That is, the Tedra bag 1 is filled with air (humidity 65%) containing a predetermined concentration of malodorous substance, and the air in the bag is supplied by the air pump 2 at a flow rate of 5 l / min to the Teflon tubes 3, 3 '. The sample taken out from the cock 4 was measured for the time-dependent concentration change (residual concentration) of the malodorous substance.

The measurement results for ammonia gas are shown in the graph of FIG. 2, and the measurement results for hydrogen sulfide gas are shown in the graph of FIG.

Example 2 In Example 1, 100 g of styrene-divinylbenzene microporous beads (Diaion HP-20) was immersed in a solution of 15 g of ethanol and 20 g of glycerin in a complex solution (100 ml) and then pulled up. The ethanol was evaporated by heating to 100 ° C. for 3 hours. Measured from the weight difference, replenish the amount of water considered to have evaporated with ethanol, and add 20 g of solution (composition: 3.7% by weight of complex, 1.8% by weight of potassium hydroxide, 79.7% by weight of water, 14.8% by weight of glycerin). Were impregnated into the microporous beads.

With respect to the contained microporous beads, the same deodorization test as in Example 1 was conducted. The measurement results for ammonia gas are shown in the graph of FIG. 3, and the measurement results for hydrogen sulfide gas are shown in the graph of FIG.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a deodorant effect testing device using the deodorant material according to the present invention. 2 to 5 are graphs showing the test results of Examples 1 and 2, respectively.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B01D 53/81 B01J 20/26 (72) Inventor Yuji Kudo 5-12 Kumeinuma Kugenuma, Fujisawa City, Kanagawa Prefecture 25 Sekine Apartment No. 6 (56) References Japanese Patent Laid-Open No. Sho 61-232856 (JP, A) Actual Development Sho 55-163022 (JP, U)

Claims (3)

[Claims] 1. A deodorant material in which an aqueous solution of a carboxyphthalocyanine metal complex is held on styrene-divinylbenzene copolymer microporous beads. 2. A deodorant material in which a styrene-divinylbenzene copolymer microporous bead holds an aqueous carboxyphthalocyanine metal complex solution and a water-absorbing substance. 3. The deodorant material according to claim 2, wherein the water absorbing substance is glycerin.