JPH0696036B2 - Composite deodorant material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composite deodorant material. More specifically, it relates to a composite deodorant material in which a deodorant is held in a composite material containing a substrate.

[Prior Art] and [Problems to be Solved by the Invention] With the improvement of living standards, there is an increasing tendency to seek a sensationally comfortable living space. Is also increasing.

Deodorants are often used by directly attaching the deodorant to various substrates. However, the use of such a deodorant is effective and durable in terms of deodorant effect. Is often not satisfied with.

Therefore, the inventors of the present invention have conducted various investigations for a deodorant material that is sufficiently satisfactory in terms of effectiveness and sustainability of the deodorant effect, and as a result, have carried out various studies, and as a result, the polymer porous membrane formed on the substrate It has been found that such a problem can be effectively solved by allowing the carboxyphthalocyanine metal complex deodorant to be held in.

A deodorant porous film in which a phthalocyanine-based metal complex deodorant is held in a polymer porous film has been proposed by the present applicant (Japanese Patent Publication No. 5-80228). Not only does the use of a quality membrane as formed on a substrate not only result in increased membrane strength, but also
It will also be possible to expand the scope of application due to compounding.

[Means for solving problems]

Therefore, the present invention relates to a composite deodorant material, which comprises a carboxyphthalocyanine metal complex deodorant held in a polymeric porous film formed on a substrate.

As the substrate, a plate-shaped body, a sheet-shaped body, a tubular body, a fibrous body, a linear body, a rod-shaped body, a lump body, a granular body, a powder body or the like made of a material such as metal, plastic, rubber, or ceramics. Any shape can be used.

The polymer porous film formed on these substrates is formed by forming a dope solution of polyvinyl butyral, polysulfone, polyvinylidene fluoride, polyvinyl acetate, polyvinyl chloride, cellulose acetate, etc. on the substrate by a dry-wet method. can get.

As the solvent used for forming the dope solution, an organic solvent which dissolves the above-mentioned polymer substance and is compatible with water, for example, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, acetone, alcohol and the like can be used.

The formation of the polymer porous membrane is performed by applying the dope solution onto the surface of the substrate by means of dipping, casting, spraying, etc., depending on the application site of the substrate, and then contacting with an aqueous medium to cause gelation. Be done.

The retention of the carboxyphthalocyanine metal complex deodorant on the polymer porous film on the substrate thus formed is generally carried out by means such as dipping, spraying or coating using a carboxyphthalocyanine metal complex deodorant solution. Although carried out, a carboxyphthalocyanine metal complex deodorant can be mixed in the dope solution in advance.

Examples of the carboxyphthalocyanine metal complex deodorant include 4,4 ′, 4 ″, 4-tetracarboxyphthalocyanine ferric iron, 4, 5, 4 ′, 5 ′, 4 ″, 5 ″, 4
, 5-octacarboxyphthalocyanine ferric iron or the like is used as an aqueous potassium hydroxide solution or the like. The amount of the carboxyphthalocyanine metal complex deodorant retained is about 1 to 10% by weight, preferably about 2 to 8% by weight, based on the weight of the porous polymer film.

〔The invention's effect〕

The composite deodorant material according to the present invention can effectively deodorize a malodorous substance in a liquid or a gas by holding a carboxyphthalocyanine metal complex deodorant in a polymer porous film.

Substances to be deodorized include malodorous substances having active hydrogen, for example, hydrogen sulfide, alkylmercaptans such as methyl, ethyl and propyl, aldehydes such as formaldehyde, acetaldehyde and butyraldehyde, and alkylamines such as ethyl, propyl and butyl. Examples thereof include indoles, skatole, and ammonia.

When deodorizing these malodorous substances, since the carboxyphthalocyanine metal complex deodorant is held in the polymer porous membrane, the contact area with the malodorous substances is increased and the deodorizing rate is increased. Furthermore, since this polymeric porous film is formed on the substrate, it is reinforced in strength and not only facilitates handling, but also expands its utilization surface.

Specific applications include, for example, structural materials, mouth cloths, textiles, futons, mats, etc., packing in columns for application in deodorizing towers, wrapping paper, wallpaper, etc.
It can be used for bran paper and applied to various pipes as deodorant pipes.

〔Example〕

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

Example 1 A 10% dimethylformamide solution of polyvinyl butyral (Wako Pure Chemical Industries, Ltd.) was applied to a glass plate (20 × 50 mm) to a thickness of 0.2 m.
Cast using a m spacer, immediately immerse in water for gelation, immerse in running water for 1 hour to remove cymethylformamide, and integrate polyvinyl butyral porous membrane on one side of glass plate A composite material was obtained.

This composite material was immersed and impregnated for 1 hour in an aqueous solution in which 5% by weight of ferric octacarboxyphthalocyanine ferric (product of Earthcrin Co., Ltd.) and its carboxyl group and an equivalent amount of potassium hydroxide were dissolved for 1 hour. Immediately soak the impregnated composite material taken out of the aqueous solution into a 0.1 molar aqueous solution of acetic acid to neutralize potassium hydroxide (pH 3.0), then sufficiently wash with water to wash the adhering acetic acid, and then at room temperature. It air-dried under the day and night.

In this way, 10 composite deodorant materials supporting ferric octacarboxyphthalocyanine ferric are stacked on the surface side porous film, put in a polyvinylidene fluoride tedra bag having a capacity of 1 and air containing 50 ppm of hydrogen sulfide ( (65% RH), the mixture was allowed to stand for 5 hours, 10 ml of air was taken out from the tedra bag with a syringe, and a sensory test was conducted. As a result, no hydrogen sulfide odor was detected.

Example 2 A glass plate (20 × 50 mm) was immersed in a 10% dimethylformamide solution of polyvinyl butyral, taken out of the solution, and then exposed to a steam flow coming out of the outlet of a home humidifier (Matsushita Electric Industrial Co., Ltd.) for 20 minutes, A composite material in which a polyvinyl butyral porous film was integrated on both surfaces of a glass plate was obtained.

With respect to this composite material, after carrying out ferric octacarboxyphthalocyanine ferric iron on both sides in the same manner as in Example 1, 5 sheets of this were piled up and deodorization of air containing hydrogen sulfide gas was carried out in the same manner as in Example 1. When the test was conducted, no hydrogen sulfide odor was sensed at all in the sensory test after 5 hours.

Example 3 Polyamide fiber Tegus (Toray rare Milan Tegus silver scale No. 1,
(Fiber diameter 0.165 mm) was dipped in a 10% dimethylformamide solution of polyvinyl butyral, and once pulled up in air, it was continuously passed through water to integrate the polyvinyl butyral porous film on the surface. A composite material was obtained.

After carrying out ferric octacarboxyphthalocyanine ferric iron on the surface side of this composite material in the same manner as in Example 1,
When 1 g of this was put in a tedra bag and a deodorizing test was conducted on the hydrogen sulfide gas-containing air in the same manner as in Example 1, no hydrogen sulfide odor was detected in the sensory test after 3 hours.

Example 4 In Example 3, a composite deodorant material was prepared by using ordinary rayon (1.5 denier manufactured by Daiwa Spinning Co., Ltd.) instead of polyamide fiber Tegus (however, it was dried in an oven at 30 ° C. after washing with acetic acid). After that, the humidity was controlled overnight in 65% RH air.) Similarly, when the air containing 100 ppm hydrogen sulfide gas was subjected to a deodorant test, the concentration was measured with a hydrogen sulfide detector tube after 30 minutes. , Its concentration had dropped to 10 ppm.

Comparative Example In Example 4, a deodorant test was conducted on ordinary rayon directly supporting ferric octacarboxyphthalocyanine, and the hydrogen sulfide concentration after 30 minutes was 40 ppm.

Example 5 In Example 4, a composite deodorizing material was prepared by using an enamel-coated wound iron wire (0.2 mm diameter) in place of the ordinary rayon, and a deodorizing test was conducted in the same manner. The hydrogen concentration had dropped to 30 ppm.

Examples 6 to 9 Stainless steel (SUS304) plate (20 x 60 x 1 mm), polyvinyl chloride piping tube (inner diameter 25 mm, outer diameter 31 mm, length 300 m)
m), polypropylene sheet (having surface treatment to improve adhesion) or high quality paper, and applying 10% dimethylformamide solution of polyvinyl butyral to these surfaces, and applying the dope solution to one side of the support. After brushing (inner surface in the case of a tube), it was immersed in water for gelation to obtain a composite material in which a polyvinyl butyral porous membrane was integrated on one surface of each support.

Regarding these composite materials, ferric octacarboxyphthalocyanine was supported in the same manner as in Example 1.

In this way, the composite deodorizing material in which ferric octacarboxyphthalocyanine ferric was carried on the porous film on one side was stacked on five stainless steel sheets, and 1 g in the case of polypropylene sheet or high-quality paper. As in the example, put it in a tedra bag, or in the case of a polyvinyl chloride tube, seal both ends with rubber stoppers covered with a tedra back sheet, and inject hydrogen sulfide gas-containing air into it. When a deodorizing test was performed on air containing 50 ppm of hydrogen sulfide gas, no hydrogen sulfide odor was detected in any of the sensory tests after 3 hours.

Example 10 In Example 1, instead of the 10% dimethylformamide solution of polyvinyl butyral, a 20% dimethylformamide solution of an aromatic polyamide (Tenex product) was used as a dope.

When a sensory test similar to that of Example 1 was performed on the obtained octacarboxyphthalocyanine ferric iron-supported composite deodorant material, no hydrogen sulfide odor was sensed at all.

Claims (5)

[Claims] 1. A composite deodorant material in which a carboxyphthalocyanine metal complex deodorant is held on a polymer porous film formed on a substrate. 2. The composite deodorant material according to claim 1, wherein the polymer porous membrane is a polyvinyl butyral porous membrane. 3. The composite deodorant material according to claim 1, wherein the substrate is a plate or sheet. 4. The composite deodorant material according to claim 1, wherein the substrate is a tubular body. 5. The invention according to claim 1, wherein the substrate is a fibrous body.
A composite deodorant material according to the item.