JPH02233138A - Deodorizing sheet - Google Patents

Abstract

PURPOSE:To form a deodorizing sheet having a fast-acting property and a lasting property by incorporating zeolite exchanged with a metal ion selected from Zn, Fe, Co, Ni, Cu, Mn, Al and Sn in a sheet material. CONSTITUTION:An aqueous solution containing one or more kind of a metal ion selected from Zn, Fe, Co, Ni, Cu, Mn, Al and Sn is brought into contact with zeolite to prepare ion exchanged zeolite. At this time, an ion exchange ratio is set so that the content of the metal ion such as Zn or the like is pref. 0.01wt.% or more and more pref. 0.1wt.% or more. A means uniformly dispersing and containing Zn-zeolite or the like in a sheet material being a fibrous material such as paper or a nonwoven fabric is adapted to form a deodorizing sheet. The amount of ion exchanged zeolite contained in the obtained deodorizing sheet is pref. 0.01-90wt.%.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is directed to odor components emitted from households, automobiles, the human body, etc., especially salt diperic malodorous gases such as ammonia and amines, hydrogen sulfide, and mercaptans. This invention relates to a deodorizing funnel containing an adsorbent effective for removing acidic malodorous gases such as.

[Prior Art] Activated carbon paper is used as a deodorizing sheet containing an adsorbent. A sheet containing zeolite (Japanese Unexamined Patent Publication No. 57-108137), a sheet containing crystalline aluminum orthophosphate (Japanese Unexamined Patent Publication No. 59-95931), and a cellulose fiber containing hydrated magnesium silicate clay mineral. (Japanese Unexamined Patent Publication No. 61-136436), Seviolite molded into paper (Japanese Unexamined Patent Publication No. 63-224734) are known.

[Problems to be solved by the invention] However, the adsorbed components contained in the deodorizing sheet do not necessarily have sufficient deodorizing performance.

For example, crystalline aluminum orthophosphate exhibits relatively good deodorizing performance against ammonia, but does not have sufficient deodorizing performance against odor components other than ammonia. Activated carbon cannot effectively adsorb and remove basic odor components such as ammonia. In addition, since the color is black and gives a feeling of uncleanness or disgust, it is not optimal for use in areas that are seen by the public, such as household or hygiene-related uses, or for applications that require a sense of cleanliness. Currently, to hide its color, it has no choice but to be covered with several layers of paper.

Natural zeolite and magnesium silicate minerals (seviolite) exhibit relatively good deodorizing performance against basic odor components such as ammonia and trimethylamine, but they exhibit relatively good deodorizing performance against acidic odor components such as hydrogen sulfide and methylmercabutane. It shows no deodorizing performance at all. Therefore, unless it is used in combination with a chemical deodorizer or the like, it will not exhibit sufficient performance as the deodorizing sheet 1.

Therefore, the present inventors have conducted extensive research with the aim of providing a deodorizing sheet containing an adsorbent that does not have such drawbacks, that is, exhibits excellent deodorizing ability that is immediately effective and long-lasting against various odor components. layered.

[Means and effects for solving the problem] The present inventors have discovered that zeolite that has been ion-exchanged with metals exhibits high adsorption properties for various malodorous substances and has excellent performance as a deodorizing agent. Patent application 1986-308789
).

Among them, Zn, Fe, Co, Ni, Cu, M
Zeolite (hereinafter referred to as Zn etc.-zeolite) ion-exchanged with one or more metal (hereinafter referred to as Zn etc.) ions selected from among n, AI and Sn is particularly excellent as a deodorizer.

By incorporating this zeolite such as Zn into a sheet, it was possible to obtain a deodorizing sheet that exhibited excellent deodorizing performance, was white or light-colored, and was stable and inexpensive.

The details will be explained below.

Zeolites, crystalline hydrated aluminosilicates containing only alkali metals or alkaline earth metals as metal ions, have very large cavities and pores not found in other minerals. The size of these pores varies depending on the type of zeolite, but is usually 3 to 9 pores, and various molecules can be trapped inside the pores. In addition, due to the influence of the electrostatic field formed by the cations inside the crystal,
Selectively adsorbs polar molecules and polarizable molecules.

On the other hand, most malodorous substances that cause malodors have a molecular weight of 200 or less. Therefore, judging from the molecular size alone, the pores of zeolite should be able to sufficiently trap malodorous substances. However, in reality, the atmosphere in which malodorous substances are present contains moisture, and zeolite selectively absorbs water molecules, which are polar molecules, and does not adsorb malodorous substances well.

This is understood to be because zeolite itself is hydrophilic, and malodorous substances that are not hydrophilic are difficult to adsorb to zeolite.

Moreover, zeolite has ion exchange ability so that it is used in applications such as builders for phosphorus-free detergents, and ions in zeolite are easily ion-exchanged with various other metal ions.

Therefore, the present inventor impregnated a zeolite such as Zn with H in the sheet 1. In other words, metal ions such as Zn were immobilized in the pores of the zeolite by ion exchange rather than supported or impregnated, and incorporated into the sheet. I thought about that.

The raw material for producing zeolite such as Zn may be either natural or synthetic zeolite, and any structure can be used as long as it has pores (3 to 9 pores) capable of adsorbing malodorous substances. As natural zeolite,
Clinobutyrolite type. Mordenite type, Chabasai 1
・Types are generally known; synthetic zeolites include A type, faujasite type (X type, Y type,
), L type, mordenite type, ZSM-5 type, etc. are industrially produced, and all are suitably used as raw materials for Zn etc.-zeolite. As is well known, zeolite exhibits a molecular sieving effect, so zeolites with large pore diameters, faujasite type, etc.
L-type etc. are preferably used.

For basic odor components such as ammonia and amines, ion-exchanged products with any metal ion such as Zn are effective. Furthermore, for acidic odor components such as hydrogen sulfide and mercaptans, zeolite ion-exchanged with Fe, Ni, Cu, Zn, etc. is preferably used. Therefore, zeolite ion-exchanged with Fe, Ni, Cu, Zn, etc. - Can be applied to both basic and acidic odor components, making it highly versatile.

By the way, there are a wide variety of odor components that are familiar to us, depending on the place where they are generated and the substance, so they are not limited to the above-mentioned basic and acidic components. For example, lower fatty acids and lower fatty acid esters are also included. To apply to malodorous gases containing these, one zeolite such as Zn should be combined with another deodorizing agent, such as a zeolite with a SIO 2 / AI 2 O 3 molar ratio of 30 or more (Japanese Patent Application No. 249,763/1983).
It can be used in combination with.

Ion exchange of zeolite is easily achieved by contacting each plate with an aqueous metal ion solution at room temperature. Although it is impossible to exchange all ions by this treatment, even if alkali metal ions and alkaline earth metal ions remain, they can be used satisfactorily in the deodorizing sheet of the present invention. The ion exchange rate is either metal ions such as Zn or 0. It is preferable that the content be 0.1 wt% or more, and 0.1 wt% or more.

Sheet materials that hold zeolite such as Zn include:
Paper 2 A fibrous material such as nonwoven fabric can be suitably used.

Embodiments of the deodorizing sheet of the present invention include sheets in which zeolite such as Zn is uniformly dispersed in the sheet material;
Zeolite such as Zn is sandwiched between the materials. Examples include sheet materials whose surfaces are coated with zeolite such as Zn. For example, Zn etc. - Zeolite! - A method of coating paper, nonwoven fabric, or other sheet materials as a coating material; A method of impregnating these sheet materials by soaking them in a zeolite slurry such as Zn.

When paper is used as a sheet material, by adding Zn-zeolite as a filler during the pulp disintegration or disintegration process, Zn-zeolite can be uniformly dispersed in the sheet material. However, any method may be used as long as zeolite such as Zn is finally dispersed and contained in the sheet.

If the content of zeolite such as Zn is low, sufficient deodorizing performance cannot be obtained, and if the content is too high, the flexibility of the sheet will generally be lost regardless of how it is added. The content must be determined. Therefore, although it varies depending on the conditions used, the amount of Zn, etc.-zeolite contained in the deodorizing sheet depends on the total O
, ranges from 1 to 90 wt%, usually 10 to 70 wt%
A range of is appropriate.

The particle size of the zeolite such as Zn contained in the sheet is 0.
, 2 to 500 μm are used.

Generally, the particle size of zeolite aggregates obtained in the production of synthetic zeolite is usually about 100 μm or less, so the deodorizing sheet of the present invention can be obtained by simply ion-exchanging the zeolite aggregates and incorporating them into a solution. In particular, when smoothness is required, the particle size must be small, and in that case, synthesis may be performed under conditions such that the particle size of the aggregate is 0.2 to 5 μm.

[Effects of the Invention] The deodorizing sheet of the present invention has a zeolite skeleton and metal ions such as Zn introduced by ion exchange, which act specifically on malodorous substances, and efficiently remove only malodorous substances from gases containing malodorous substances. It is captured and deodorized. Once captured, malodorous substances are not easily desorbed and are immobilized on the zeolite.

Therefore, it can remove malodorous substances more powerfully and instantly than other deodorizing sheets.

Further, the deodorizing sheet of the present invention is white or light-colored,
There is no feeling of disgust or uncleanness. Furthermore,
By selecting Cu, Zn, Fe, etc. as the metal ion, it is possible to change the color to dark as the amount of malodorous substances captured increases. As a result, the deodorizing agent itself becomes an indicator, indicating the deterioration of the deodorizing sheet's performance and letting you know when to replace it.

Furthermore, the deodorizing sheet of the present invention exhibits its performance even when moisture is contained in malodorous gas.

Therefore, the deodorizing sheet according to the present invention has a wide range of uses, such as for general household use such as wallpaper, shoji paper, and shoe insoles, and for removing odors generated from the human body such as in automobiles and hygiene-related products. This enables a wide range of applications.

[Example code] Specific examples of this invention are shown below.

Metal ion exchange of zeolite> Pure water was added to Y-type, L-type, and mordenite-type zeolites to form a slurry with a solid content concentration of 20 wt%. Metal ion exchange of the zeolite was performed by adding copper sulfate, cobalt sulfate and zinc sulfate to this slurry and mixing at room temperature for 30 minutes. Filter this slurry and
Rinse with water until 4 ions are no longer detected, dry at 100°C for several hours, and then dry at 80% relative humidity. A metal ion-exchanged zeolite in a permanent state was obtained by standing overnight under ambient air.

The zeolites used for these are as follows.

Cu-Y and Co-Y are obtained by ion-exchanging artificially synthesized sodium/lium Y type zeolite with copper sulfate and 1'Il cobalt arsenate, respectively.

Cu-M is obtained by ion-exchanging artificially synthesized sodium mordenai 1 type zeolite I with copper sulfate.

Zn-L is obtained by ion-exchanging artificially synthesized potassium L-type zeolite with zinc sulfate.

These metal ion-exchanged zeolites were used as deodorized paper fillers in the present invention.

Table 1 shows S i O determined by atomic absorption method.
2/AI■03 molar ratio, metal content and water content are shown.

Table 1 Other fillers> In order to compare with the deodorizing sheet of the present invention, sheets were prepared using the following adsorbents as fillers.

As a synthetic zeolite, sodium Y-type zeolite (
In the table, Na-Y) was used.

Natural zeolite is mordenite manufactured by Kunimine Industries, which is crushed in an agate mortar (Kunimine in the table).
It was used.

As a clay mineral, a fibrous magnesium silicate mineral called Seviolite (trade name "Ade Plus" manufactured by Showa Mining Co., Ltd.) was fired at 600°C for 20 minutes (in the table, Sepiolai 1) was used as a filler. used.

Preparation of deodorizing sheet> 10 g of Ting-U Paper (trade name: Kleenex J, manufactured by Jujo Kimberly Co., Ltd.) and 490 g of pure water were subjected to f.1ε.
Household juicer mixer (Toshiba MX-2)
9 4 G type) for 20 minutes. Thereafter, the mixture was cooled to 20° C. with running water, 10 g of filler and 0.3 g of a sizing agent (carboxymethyl cellulose) were added, and further mixed and disintegrated for 20 minutes using a household juicer mixer.

Weigh out 240g of the vulp slurry obtained in this way.3
00maX450mm stainless steel bag 1
・It was spread out to a uniform thickness and dried at 120°C for about 4 hours. After drying, remove the paper from the vat at 211 A'
A deodorizing sheet was prepared and used as a sample for measuring deodorizing performance.

Usage Examples 1 to 4, Comparative Examples 1 to 3 100 mg of the deodorizing sheet was placed in an Erlenmeyer flask with a content of fa 6 2 mA and the flask was stoppered. Inject 2 mA of 9.68 vol% ammonia gas into this Erlenmeyer flask using a gas tight syringe, and measure the ammonia gas concentration in the Erlenmeyer flask after 2, 12, and 30 minutes using Gas Chroma! - Quantitated by graphography (detector: TCD). Further, for comparison, similar measurements were performed on a blank. Table 2 shows the results.
Shown below.

In Usage Examples 1 to 4 and Comparative Example 3, ammonia was no longer detected after 2 minutes. On the other hand, in Comparative Examples 1 and 2, ammonia was detected even after 30 minutes.

Table 2 Ammonia adsorption performance Usage examples 5 to 8, Comparative examples 4 to 6 60 mg deodorizing sheet with an internal volume of 62 m! Pour into an Erlenmeyer flask and stopper. 10. 2.5 volumes of Ovol 96 trimethylamine was injected into the Erlenmeyer flask using a gastight syringe, and the trimethylamine concentration in the Erlenmeyer flask after 2, 12, and 30 minutes was determined by gas chromatography (detector 2 FID). Also, for comparison,
A similar fllll determination was performed on the blank. The results are shown in Table 3.

After 2 minutes in usage examples 5 and 7, and 12 minutes in usage examples 6 and 8.
Trimethylamine was no longer detected after minutes. On the other hand, in Comparative Examples 4 to 6, trimethylamine was detected even after 30 minutes.

Table 3 Trimethylamine adsorption performance A 60 mg deodorizing sheet was placed in an Erlenmeyer flask with an internal volume of 62 ml and the flask was stoppered. Inject 2 mA of 9.82 vol% methyl mercabutane into the Erlenmeyer flask using a gastight syringe, and measure the methyl mercabutane concentration in the Erlenmeyer flask after 2 minutes, 12 minutes, and 30 minutes by gas chromatography (detector zFID).・It was quantified by. In addition, for comparison purposes, a similar 4p1 determination was performed on a blank. The results are shown in Table 4.

Methyl mercabutane was no longer detected in Use Example 9 after 12 minutes and in Use Example 1o after 30 minutes. On the other hand, in Comparative Examples 7 to 9, methylmercaptan was detected even after 30 minutes had passed, and it was determined that methylmercaptan was not adsorbed at all.

Usage Examples 9 and 10, Comparative Examples 7 to 9 Table 4 Adsorption performance of methyl mercabutane or higher. Comparative examples of deodorizing seals containing Na-Y, Seviolite, and Kunimi zeolite showed slight rock adsorption against ammonia and trimethylamine. However, it does not adsorb methyl mercabutane at all. In contrast, in the example of use according to the present invention, any odor components can be well adsorbed and deodorized in a short time.

Claims (2)

[Claims] (1) A deodorizing sheet containing zeolite ion-exchanged with one or more metal ions selected from Zn, Fe, Co, Ni, Cu, Mn, Al, and Sn. (2) The content of ion-exchanged zeolite is 0.1~
The deodorizing sheet according to claim (1), which has a content of 90 wt%.