WO1994023764A1

WO1994023764A1 - Deodorant, gas-permeable deodorized film and method of manufacturing the same

Info

Publication number: WO1994023764A1
Application number: PCT/JP1994/000641
Authority: WO
Inventors: Susumu Yamazaki
Original assignee: Kabushiki Kaisha Ikueisha; Aso Seiyaku Kabushiki Kaisha
Priority date: 1993-04-19
Filing date: 1994-04-18
Publication date: 1994-10-27
Also published as: JPH06296672A; AU6513394A

Abstract

This invention relates to a deodorant capable of deodorizing a basic malodorous gas and an acidic malodorous gas simultaneously. It has been demanded that a deodorant having a large deodorization effect with respect to a malodorous gas in which a basic malodorous gas and an acidic malodorous gas coexist in a mixed state, a malodorous gas containing a neutral malodorous gas having a sulfur compound as a component thereof, or a styrene gas as well be developed. The present invention is directed to a deodorant consisting of a powdered mixture in which activated clay and a basic substance or/and a neutral as main components coexist, or a gas-permeable deodorized film formed by kneading this mixture with a resin material and molding the resultant product to a film type body, and a deodorant capable of being used conveniently for medical and domestic purposes, or a gas-permeable deodorized film.

Description

Specification

Technical field of deodorizing material, breathable deodorizing film and method for producing the same.

The present invention relates to a deodorizing material, a gas permeable deodorizing film, and a method for producing the same. More specifically, the present invention relates to a solid acid, activated clay, and a basic substance or a neutral substance used for medical or household use. The present invention relates to a breathable deodorizing film having breathability, which can be suitably used as a sheet or a deodorant blended with zinc oxide, and a method for producing the same.

Background technology

Conventionally, deodorizers are physically adsorbed deodorizers that utilize the physical adsorption phenomenon due to their large surface area, such as activated carbon and silica gel, and chemicals that utilize chemical reactions such as neutralization, oxidation, and reduction of inorganic metal salts. There are known deodorizing materials, plant-based deodorizing materials containing tree extract as a main component, and bio deodorizing materials utilizing the biochemical activity of bacteria.

In addition, as a breathable deodorizing film, a deodorizing material, for example, activated carbon, porous silica, or a mixture of a metal salt and alkopenic acid is kneaded with, for example, a polyethylene resin, which is rolled and formed into a sheet. After melt-forming a fluorinated film or a polyolefin resin, a filler and a radical generator as proposed in JP-A-2-309969, and an olefin resin composition containing a deodorant or a fragrance Stretched breathable deodorant or fragrance films are known.

Hereinafter, in the present invention, the odor that is generally avoided among the odors is referred to as an odorous gas.

The malodorous gases include basic gases such as ammonia and trimethylamine (hereinafter referred to as basic malodorous gases), and acid gases such as hydrogen sulfide and methyl mercaptan (hereinafter referred to as acidic malodorous gases). Neutral gases such as methyl sulfide, methyl disulfide, and acetoaldehyde (hereinafter referred to as neutral odor gases) can be broadly classified. There are also non-odorous odorous gases such as styrene. Usually, several types of odorous gas are mixed in the odorous gas.

Disclosure of the invention It is said that there are about 400,000 types of odorous components, and in order to be sensed by olfaction, it must be volatile, hydrophilic, or lipophilic with a carbon number of about 300 or less. .

Table 1 shows the statutory odorous substances that are the main cause of odor pollution and are often used for measuring the deodorizing effect.

table 1

Usually, it is said that many offensive odor gases are composed of several types of these odorous gases.

These deodorizing technologies for deodorizing odorous gases include:

① Chemical reaction deodorization

② Adsorption and deodorization

③ Biological deodorization

感覚 Sensory deodorization

Is mentioned.

Deodorizing materials have many deodorizing effects, and were selectively used depending on the application.

When developing new deodorizers, the search for substances with stronger deodorizing capabilities or the development of systems that combine known deodorants to enhance deodorizing capabilities has been adopted. In addition, it will be crucial whether the developed deodorizing products can bring the deodorizing ability and product cost to market. In addition, the properties of acidic and basic malodorous gases are extremely contradictory. Therefore, it is extremely unlikely that only a specific deodorizing material will effectively act on both malodorous gases.

The present invention solves such a problem, and is applicable to a malodorous gas in which a basic malodorous gas and an acidic malodorous gas are mixed, and a neutral malodorous gas in which a neutral malodorous gas containing a sulfur compound is mixed, or styrene gas. The present invention also proposes a deodorizing material exhibiting an effective deodorizing effect, a breathable deodorizing film, and a method for producing a breathable deodorizing film. -'

The present inventor has conducted intensive studies to solve such problems, and as a result, has an activity widely used in the final finishing process of petroleum products, particularly lubricating oils, as having a strong physicochemical activity and as an inexpensive deodorant. Focusing on the clay, there is no chemical reaction even if a basic substance and a neutral substance coexist in the same system where the activated clay exists, and the deodorizing effect can be maintained. It is found that basic substances such as calcium carbonate and calcium hydroxide and neutral substances of zinc oxide are optimal as components having heat resistance when kneading, then rolling into a sheet and further stretching. The present invention has been completed and the present invention has been completed.

The deodorizing material of the present invention is characterized by comprising a powdery mixture containing activated clay and a basic substance or Z and a neutral substance as main components and coexisting them. The other deodorizing material is a deodorizing material in which activated clay or activated clay and a basic substance or Z and a neutral substance are the main components, and a powdered mixture in which they coexist is wrapped in a nonwoven fabric or a porous film.

Still another deodorizing material is a film-shaped deodorizing material in which activated clay and a basic substance and / or a neutral substance are kneaded with a polyolefin resin.

Further, the breathable deodorizing film of the present invention is characterized by comprising a sheet obtained by melt-molding a polyolefin resin composition in which activated clay and a basic substance or Z and a neutral substance coexist, and then stretching.

Further, the present invention proposes a method for producing a breathable deodorized film, which comprises kneading activated clay and a basic substance and / or a neutral substance into a polyolefin resin, and then melting the mixture to form a film. It is characterized by forming and stretching the film.

The activated clay has acidity lO SOm.e.Z lOOg specific surface area of 150 to Activated clay of 300 m ² / g may be used. The basic substance may be at least one of calcium carbonate and calcium hydroxide, and the neutral substance may be zinc oxide.

Activated clay, basic substance or neutral zinc oxide or activated clay, and basic substance and zinc oxide coexist in the deodorizer. Basic malodorous gas in the atmosphere is active. It is deodorized by clay, acid malodorous gas is deodorized by basic substances, and neutral malodorous gas and basic malodorous gas containing sulfur compounds are deodorized by zinc oxide.

In addition, the activated clay, a basic substance or a zinc oxide or an activated clay, a basic substance and zinc oxide coexist in the air-permeable deodorizing film Φ, and the film has an air permeability. Therefore, basic malodorous gas in the atmosphere is deodorized by activated clay while passing through the film, and acidic malodorous gas is deodorized by basic substance while passing through the film. Neutral odorous gas and basic odorous gas containing as components are deodorized by zinc oxide while passing through the film.

When the deodorizing material of the present invention is used, since activated clay and the basic substance or Z and the neutral substance coexist, there is an effect that a plurality of types of malodorous gases can be simultaneously deodorized. .

In the case of using the breathable deodorizing film of the present invention, since activated clay and a basic substance or a neutral substance and a neutral substance coexist in the stretched film, a plurality of types of malodorous gases pass through the film. At the same time, it has the effect of being able to deodorize at the same time.

Further, according to the method for producing a gas-permeable deodorizing film of the present invention, when a plurality of types of malodorous gases pass, the air-permeable property can be simultaneously deodorized with activated clay and a basic substance or a neutral substance and a neutral substance. This has the effect that the film provided can be easily manufactured.

BRIEF DESCRIPTION OF THE FIGURES

Fig. 1 Characteristic diagram showing the relationship between montmorillonite activation conditions and acidity or specific surface area.

Fig. 2 Characteristic diagram showing the relationship between the acidity of activated clay and the decolorizing ability.

FIG. 3 is a partially cutaway perspective view showing one embodiment of the deodorizing material of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION First, the activated clay, basic substance, and neutral substance used in the deodorizing material and the breathable deodorizing film of the present invention will be described.

Activated clay is an A1—Si-based gel substance, which elutes soluble substances in the structure of montmorillonite, for example, by activating the montmorillonite or halloy site, for example, by treating it with sulfuric acid. It has a surface with fine pores, its specific surface area is 150-300 m ² / g, and the average diameter of the pores is about 50 people. By changing the activation conditions, the activated clay can reduce the acidity and specific surface area as a solid acid as shown in Fig. 1 (quoted from Japan Activated Clay Co., Ltd., catalog “Activated Clay”). Can be controlled.

In the activation treatment, part of the cations are exchanged for hydrogen ions due to the activation treatment, so that the cations have a displaceable hydrogen, and the amount thereof reaches 10 to 30 m.e./I 00 g, for example, as shown in FIG. Under activation conditions, it shows characteristic values of an activity of 30 m.e./100 g and a specific surface area of 250 m ^: / g. By changing the activation conditions in this way, the acidity and the specific surface area change, indicating a chemical activity not found in other adsorbents.

In addition, the adsorption properties of activated clay on the surface of activated clay are selective, and in the state where several substances coexist, see Fig. 2 (quoted from Japan Activated Clay Co., Ltd., catalog “Activated Clay”). As shown, it shows a selective adsorption capacity for polar substances, unsaturated substances and aromatic substances.

The physical properties of activated clay as a deodorizer can be summarized as follows.

(1) It is a solid acid that has displaceable hydrogen on its surface and has a high acidity of 10 to 30 me / 100 g. A solid acid is a substance having an acid activity in a non-polar solvent, and exhibits a strongest deodorizing function against a basic gas such as ammonia due to the strong acid activity.

(2) It has surface characteristics with an average pore diameter of 50 people and a specific surface area of 150 to 300 m ² / g. (3) The characteristics of (1) and (2) can be controlled by changing the activation conditions, and have a chemical activity not found in other adsorbents.

④ It has strong selective adsorption capacity especially for polar substances, unsaturated substances and aromatic substances.

Most of the malodorous gases, except for styrene, are polar substances, so activated clay is selectively adsorbed in ascending order of polarity. In addition, the activity as a solid acid strongly affects basic odorous gases such as ammonia, and its deodorizing effect is extremely high. Big.

In addition, by changing the activation conditions, the specific surface area and the acidity can be changed, and optimum adsorption characteristics can be obtained for a plurality of types of malodorous gases.

Also, since styrene is an aromatic hydrocarbon, activated clay has strong adsorption characteristics.

In the present invention as adapted to use the acidity 1 0-30111. 6. / 1 00, specific surface area 1 50 activity clay ~300m ² / g. ''

This activated clay can be determined by examining the activation conditions to determine the largest adsorption property of activated clay, in contrast to the physical properties (polarity, molecular weight, molecular structure, etc.) of various neutral malodorous gases. Because.

The most effective means to treat another acidic malodorous gas, which is important as a target of deodorization, is to remove these acidic malodorous gases by neutralizing them with a basic substance. It is.

This is already a known measure.

Therefore, if a basic substance can be made to coexist in the same system where the activated clay is present, this coexistence is not only caused by basic odor gas such as ammonia and trimethylamine, but also by hydrogen sulfide and methyl mercaptan. The present inventor paid attention to the fact that it would be an effective means for acidic malodorous gas, and made various studies on basic substances that can coexist with activated clay.

For a breathable deodorizing film in which activated clay and a basic substance or a neutral substance coexist, the basic substance must have a large deodorizing function and be a substance capable of forming the film's permeability. is important.

Therefore, calcium carbonate (C a C 〇 ₃ ) is the most suitable substance for both deodorizing function and formation of air permeability. To further increase the deodorizing function, calcium hydroxide, a strong basic substance of pH 12 is used. It was sufficient to mix a small amount of calcium (Ca (OH) 2), and it was confirmed that these three substances could coexist in the same system. Therefore, by coexisting activated clay and calcium carbonate as a basic substance in the same system, and coexisting calcium hydroxide in the same system, for example, a basic malodorous gas such as ammonia can be obtained. For example, an acidic malodorous gas such as hydrogen sulfide can be most reliably deodorized at the same time.

Calcium carbonate is microporous made of air-permeable synthetic resin. It is the most effective filler for SPF (abbreviated as MPF), and is a basic substance with a pH value of 9. The combination of calcium carbonate and activated clay coexists in the breathable deodorant film. This is the best deodorizing material to be used. '

In addition, zinc oxide (ZnO), a neutral substance, is known to be effective as a filler for microporous films, but also has extremely high reactivity with sulfur. Substance.

Therefore, various experiments were conducted on microporous films in which activated clay and zinc oxide coexisted. Hydrogen sulfide (H ₂ S), methyl sulfide ((C

It was found that the odorous gas containing sulfur compounds such as H ₃ ) ₂ S) could be deodorized. .

Next, the malodorous gas that can be deodorized by a deodorizing material in which activated clay (solid acid) monobasic substance, zinc monoxide, which is the essence of the present invention, coexists in the same system will be described below.

① Activated clay styrene

Activated clay Basic odorous gas such as ammonia

Activated clay ^ Neutral odorous gas with large polarity

② Basic substance → acidic odorous gas

③ Zinc oxide → odorous gas containing sulfur compounds, eg H ₂ S.

In addition, the deodorizing material according to the present invention does not cause a chemical reaction with activated clay and a basic substance or a neutral substance as long as it is a solid substance that is effective as a deodorizing substance for a certain kind of odor (gas). Most of them can coexist with activated clay and basic or neutral substances.

The mixing ratio of the various deodorizing materials may be appropriately set according to the type of the malodorous gas to be deodorized.The basic or neutral substance is about 90 to 50 parts by weight with respect to 10 to 50 parts by weight of activated clay. do it.

In the case of a deodorizing material wrapped in a nonwoven fabric or a porous film, activated clay, calcium carbonate, calcium hydroxide, and the like having a particle size large enough not to pass through the holes formed in the nonwoven fabric or the porous film It is necessary to use zinc oxide. In this case, the activated clay, calcium carbonate, calcium hydroxide, and zinc oxide are graded according to the production method and classification method, and may be appropriately selected from the grades. As the polyolefin resin for kneading activated clay, or activated clay and a basic substance, or activated clay and a neutral substance, these are kneaded with the resin, molded into a sheet, and further processed into a sheet. Considering the balance between the air permeability imparted by stretching in the uniaxial or biaxial direction and the deodorizing effect of the kneaded activated clay and basic substance, or the coexistence of activated clay and neutral substance, Polyethylene is preferred.

For example, the mixing ratio of the deodorizing agent consisting of activated clay and a basic substance to the polyolefin resin is 44 to 48 parts by weight in consideration of sufficient deodorizing power and good air permeability. The polyolefin resin is in the range of about 56 to 52 parts by weight.

Next, specific examples of the deodorizing material of the present invention will be described together with comparative examples.

Example 1

This embodiment is an embodiment of the deodorizing material according to claim 1.

Activated clay with an acidity of 30m.e.Zl 00g and specific surface area of 250m ² / g (Nippon Activated Shirato Co., Ltd., powdered activated clay), and calcium carbonate (Shiraishi calcium) as a basic substance Manufactured by Whiteton SSB Red), calcium hydroxide (manufactured by Ryoko Lime Industry Co., Ltd., special name slaked lime) and zinc oxide as a neutral substance (manufactured by Seido Chemical Co., Ltd., active under the trade name) Zinc white) was mixed as shown in Table 2 to prepare a deodorizing material consisting of a powdery mixture having an average particle size of 2 in to 5 μιη in which activated clay and a basic substance or zinc oxide coexisted. Activated clay has a particle size distribution of 95% or less with a particle size of lOm or less.

Then, a deodorization test was performed for each of the prepared deodorizing materials. For the deodorization test, 1 g of deodorizing material was put into a 500 ml flask, 300 ppm ammonia gas was sealed in the flask, the opening of the flask was sealed, and after 60 minutes, the ammonia gas in the flask was The remaining gas concentration was measured. Table 2 shows the measurement results.

Separately from ammonia gas, a deodorizing test (residual gas concentration measurement) was performed on hydrogen sulfide gas of 20ρρπι by the same method. The results are shown in Table 2.

The residual gas concentration was measured with a Kitagawa detector tube.

Comparative Example 1

Activated clay (made by Nippon Activated Clay Co., Ltd. Clay), calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name Whiteton SSB Red), calcium hydroxide (manufactured by Ryoko Lime Industry Co., Ltd., trade name: slaked lime), zinc oxide (manufactured by Seido Chemical Co., Ltd.) Table 2 shows the residual concentrations of ammonia gas and hydrogen sulfide gas of this comparative deodorant under the same conditions as in Example 1 above. The measurement results are shown in Table 2. .

Table 2

As is clear from Table 2, it was confirmed that the deodorizing material of the present invention had an excellent deodorizing effect on ammonia gas and hydrogen sulfide gas. On the other hand, the deodorizing material of Sample 6 (activated clay alone) of Comparative Example 1 had an excellent deodorizing effect on ammonia gas, but had no deodorizing effect on hydrogen sulfide gas. The deodorizing materials of Sample 7 (a mixture of calcium carbonate and calcium hydroxide) and Sample 8 (zinc oxide alone) of Comparative Example 1 have excellent deodorizing effects on hydrogen sulfide gas, There was no deodorizing effect on ammonia gas.

Example 2

Sample number of the above Example 1 except that the activated clay used was 15 m.e.Zl00 _{g of} acidity and a specific surface area of 300 m ² / g (trade name: activated clay made by Nippon Active Shirato Co., Ltd.). Deodorizing materials similar to 2, 3, 4, and 5 were prepared.

When the residual concentrations of ammonia gas and hydrogen sulfide gas were measured for this deodorizing material under the same conditions as in Example 1, the residual amount of ammonia gas was 0 ppm, and the residual amount of hydrogen sulfide gas was 0 ppm. Was.

Therefore, it was confirmed that the deodorizing material of this example had an excellent deodorizing effect on ammonia gas and hydrogen sulfide gas as in Example 1. Example 3

This embodiment is an embodiment of the deodorizing material according to claim 2.

Acidity 30m. E. Roh i OOg, a specific surface area of 250m ² / g of activated clay (Japan active white earth Co., Ltd., trade name powdered activated clay) and, as a basic substance carbonate calcium © beam (white ' Made by Seki Calcium Co., Ltd., brand name Whiteton SSB red), calcium hydroxide (manufactured by Ryoko Lime Industry Co., Ltd., trade name special slaked lime) and zinc oxide as a neutral substance (manufactured by Seido Chemical Co., Ltd. As shown in Table 3, a deodorizing material consisting of a powdery mixture having an average particle size of 50 111 to 100 ^ 111 in which activated clay and a basic substance or zinc oxide coexist was prepared. Was.

Then, as shown in FIG. 3, 5 g of the prepared deodorizing material 1 was filled in a bag-shaped container 2 made of a non-woven fabric (manufactured by Nichiei Industry Co., Ltd., trade name: Tapils) having a size of l Ocm X 10 cm.

Then, a deodorizing test was performed for each of the deodorizing materials.

In the deodorizing test, a deodorizing material wrapped in a nonwoven fabric was suspended in the flask. Then, 300 ppm ammonia gas and 20 ppm hydrogen sulfide gas were simultaneously sealed in the flask, the opening of the flask was sealed, and after 60 minutes passed, the residual gas concentrations of ammonia gas and hydrogen sulfide gas in the flask were measured. did. Table 3 shows the measurement results.

The residual gas concentration was measured with a Kitagawa detector tube.

Comparative Example 2

Activated clay (manufactured by Nippon Activated Clay Co., Ltd., trade name powdered activated clay), calcium carbonate (manufactured by Shiraishi Callitech Co., Ltd., trade name: Whiteton SSB Red) and calcium hydroxide (Ryoko Lime Industry Co., Ltd.) Co., Ltd., trade name special hydrated lime) and zinc oxide (manufactured by Seido Chemical Co., Ltd., trade name: activated zinc flower) shown in Table 3 were used. The residual concentrations of gas and hydrogen sulfide gas were measured, and the measurement results are shown in Table 3.

Deodorizing material string Jl

Dissolved gas concentration (P p m)

Activated clay Calcium carbonate Calcium hydroxide i-lead

Ammonia gas Hydrogen sulfide gas Sample 9 4 0 6 0 2 0 6 Sample 1 0 4 0 5 0 1 0 2 0 1 Example 3 Sample 1 1 3 0 7 0 3'0 1

Sample 1 2 3 0 1 0 6 0 3 0 1 Sample 1 3 4 0 3 0 3 0 2 0 1 Sample 1 4 1 0 0 1 5 9 Relative 2 Sample 1 5 8 0 2 0 2 8 0 1

Sample 1 6 1 0 0 2 6 0 1

Three As is clear from Table 3, it was confirmed that the deodorizing material of the present invention (the deodorizing material filled in the non-woven bag-like container) had an excellent deodorizing effect on ammonia gas and hydrogen sulfide gas. On the other hand, the deodorizing material of Sample 14 (activated clay alone) of Comparative Example 2 (deodorizing material filled in a non-woven bag-like container) has a good deodorizing effect on ammonia gas, while hydrogen sulfide gas The deodorizing effect on was poor. In addition, the deodorizing material of Sample 15 (a mixture of calcium carbonate and calcium hydroxide) and the deodorizing material of Sample 16 (zinc oxide alone) of Comparative Example 2 have extremely good deodorizing effects on hydrogen sulfide gas. However, there was no deodorizing effect on ammonia gas.

Example 4

Sample No. 1 of Example 3 except that a bag-like container made of a porous film (Santama Leather Co., trade name: Sambic, 80 / m thickness) was used instead of the nonwoven fabric as the material to wrap the deodorizing material. A deodorizing material similar to that of 0, 11, 12, 13 was prepared.

When the residual concentration of ammonia gas and hydrogen sulfide gas was measured under the same conditions as in Example 3 above, the residual amount of ammonia gas was 20 to 30 ppm, and the residual amount of hydrogen sulfide gas was 1 to 2 ppm. Met.

Comparative Example 3

Sample No. 1 of Comparative Example 2 described above except that a bag-like container made of porous film (trade name: Sanvic, thickness: 80 μππι) was used instead of the nonwoven fabric as the material to wrap the deodorizing material. Comparative deodorizers similar to 4, 15, and 16 were prepared.

When the residual concentrations of ammonia gas and hydrogen sulfide gas were measured for this comparative deodorant under the same conditions as in Example 3, the residual amounts of ammonia gas were 15 ppm and 280 ppm, and the residual amounts of hydrogen sulfide gas were 9 ppm and lppm.

Therefore, it was confirmed that the deodorizing material wrapped in the nonwoven fabric or the porous film of the present invention had an excellent deodorizing effect on ammonia and hydrogen sulfide gas. On the other hand, the non-woven fabrics of Comparative Examples 2 and 3 and the deodorizing material wrapped in the porous film had a deodorizing effect on only one of the ammonia gas and the hydrogen sulfide gas. At the same time, no deodorizing effect was obtained. Example 5

This embodiment is an embodiment of the deodorizing material according to claim 3. .

Acidity SOm.e.ZlOOg, Activated clay with a specific surface area of 250m ² / g (Nippon Activated Shirato Co., Ltd., powdered activated clay) 400g, Calcium Carbonate (Shiraishi Rushidum Co., Ltd., White Ton) 300 g of SSB red), 200 g of calcium hydroxide (trade name of slaked lime manufactured by Ryoko Lime Industry Co., Ltd.) and 300 g of zinc oxide (trade name activated zinc flower manufactured by Seido Chemical Co., Ltd.) are made of polyolefin resin ( The mixture was kneaded with 1000 g of a commercial product “Nakoxelen 200) manufactured by Sumitomo Chemical Co., Ltd., and then rolled into a sheet having a thickness of 80 μιη to prepare a film-like deodorizing material. Then, a deodorizing test was performed on the prepared film-like deodorizing material.

In the deodorization test, five pieces of film-shaped deodorizing material (10 cm x 10 cm) were inserted into a 500-m1 flask, suspended, sealed with 300 ρππ ammonia gas in the flask, and the opening of the flask was opened. After sealing for 60 minutes, the residual gas concentration of ammonia gas in the flask was measured, and the residual amount was found to be 40 ppm.

In addition, a deodorizing test (residual gas concentration measurement) of 20 ppm of hydrogen sulfide gas separately from ammonia gas by the same method showed that the residual amount was 3 ppm.

Therefore, it was confirmed that the deodorizing material of this example had a deodorizing effect on ammonia gas and hydrogen sulfide gas as in Example 1. '' Example 6

This embodiment is an embodiment of the breathable deodorizing film according to claim 6. The breathable deodorizing film of this example was prepared by the following method (an example of claim 9 of the present invention).

Activated clay with an acidity of 30m.e.Z 100g and specific surface area of 250m ² / g (Nippon Activated Shirato Co., Ltd., powdered activated clay) and calcium carbonate as a basic substance (Shiraishi Calcium Co., Ltd. Whiteton SSB red), Hydroxidizing power Rushidum (manufactured by Ryoko Lime Industry Co., Ltd., special name slaked lime), and zinc oxide as a neutral substance (manufactured by Shodo Chemical Co., Ltd., active zinc flower) ) And polyolefin resin (linear polyethylene resin (trade name: Exelen 200, manufactured by Sumitomo Chemical Co., Ltd., density: 0.90, M.I.20, .P.115 ° C)) and branched low-density polyethylene. Resin (Sumitomo Chemical Co., Ltd., trade name Sumicaro (GZ801, Density 0.92, I.20, P.121 ° C) 3: 1) as shown in Table 4 and melted at 230 ° C with an extruder. The resulting pellets were extruded into pellets, and the pellets were rolled by a roller to produce a 200 μm thick sheet. '

The rolled sheet thus prepared was uniaxially stretched by a stretching machine to prepare a breathable deodorized film composed of a stretched film having a thickness of 70 μιη.

Then, a deodorization test was performed for each of the created breathable deodorizing films.

For the deodorization test, insert a gas permeable deodorizing film (size 10 cm x 10 cm) into the flask, suspend it, fill the flask with 300 ppm ammonia gas, seal the opening of the flask, and wait 60 minutes. Thereafter, the residual gas concentration of the ammonia gas in the flask was measured. Table 4 shows the measurement results.

Separately from ammonia gas, a deodorizing test (residual gas concentration measurement) was also performed on 20 ppm of hydrogen sulfide gas in the same manner. Table 4 shows the results.

The residual gas concentration was measured using a Kitagawa detector tube.

In addition, the measurement of the air permeability conformed to JIS P118.

Comparative Example 4

A method similar to that of Example 6 was used except that Pansil (trade name, organic acid extracted from persimmon astringent) was used instead of activated clay, and the ratio to polyolefin resin was as shown in Table 4. A breathable deodorizing film was made.

The air permeability and the residual concentrations of ammonia gas and hydrogen sulfide gas of the breathable deodorized film thus prepared were measured under the same conditions as in Example 6, and the measurement results are shown in Table 4.

Comparative Example 5

Calcium carbonate (Shiroishi Calcium Industry Co., Ltd., trade name Whiteton SSB Red) was used as the deodorizing material without using activated clay at all, and the above procedure was performed except that the ratio to polyolefin resin was set to Table 4. A breathable deodorizing film was prepared in the same manner as in Example 6.

Then, the air permeability and the residual concentrations of ammonia gas and hydrogen sulfide gas of the created gas permeable deodorizing film were measured under the same conditions as in Example 6 above.

, 1 is 'R;'; |

Hydroxylation Oxidation Polystyrene Permeable 1 gas ^ (Ρ m)

. Excitation Ί tens force Rushiumu Kanoreshiuno, ΊΙΪ, full fin i; U Jli'i (scc / IOOcc ) Ύ Nmoniagasu hydrogen sulfide department gas施例^{(i:. \ 1 7 6.} 0 A 8. 0 Λ (; 0 B 0 () 1, () 0

: \ 1 8 B. () 00. 0 3/1. 0 80 1 () 0

1.9 Bansyl 10.0 A 0.0 50. 0 550 18 () 3 Bans 1.0. 0 (; 9.0 Γ) (; 0 8 () 0

Comparative example 5 m ^: 21 60.0 A 0.0 0) Γ) 0? , 0 () 3

^ Factoryπi4 As is clear from Table 4, it was confirmed that the breathable deodorizing film of the present invention had an excellent deodorizing effect on ammonia gas and hydrogen sulfide gas. In addition, it has been confirmed that it has excellent air permeability because it has high air permeability. On the other hand, the air-permeable deodorizing film of the comparative example has excellent air-permeability but has a very low deodorizing effect on ammonia gas, and when it contains a plurality of types of malodorous gases (here, ammonia gas and hydrogen sulfide gas), Cannot respond to deodorization treatment.

The activated clay used in the present invention has a unit price of 200 yen / kg, the unit price of calcium carbonate coexisting with the activated clay in the same system is 300 yen / kg, and the unit price of calcium hydroxide is 150 yen / kg. kg, and the unit price of zinc oxide is 300 yen Zkg, so the unit price of the deodorizer that can be combined with them is 200-300 yen / kg, which is a typical flavonoid deodorant of the conventional deodorant (unit price). The cost is extremely low compared to 2,500 to 3,500 yen (Zkg), and it is economical.

Claims

The scope of the claims .

I. A deodorizing material characterized by comprising a powdered mixture containing activated clay and a basic substance or a neutral substance and a neutral substance as main components and coexisting with the same.

2. A deodorizing material in which activated clay or activated clay and a basic substance and / or a neutral substance are used as main components, and a powdered mixture in which the clay is present is wrapped in a nonwoven fabric or a porous film.

3. A film-like deodorizer made by kneading activated clay and a basic substance or Z and a neutral substance with a polyolefin resin.

4. The activated clay acidity 10～30111,6. 10 (^, of claims, characterized in that a specific surface area 150 ~300m ² / g first term to the third term of any one Deodorant.

5. The basic substance is at least one of calcium carbonate and calcium hydroxide, and the neutral substance is zinc oxide. Deodorizing material described in.

6. A breathable deodorizing film comprising a sheet obtained by melt-molding a polyolefin resin composition in which activated clay and a basic substance and / or a neutral substance coexist, and then stretching the sheet.

7. The activated clay acidity 10 to 30 m. E. Roh 100 g, breathable deodorizing film according to claim 6, wherein, characterized in that the specific surface area 150 ~300m ² / g.

8. The air-permeable material according to claim 6, wherein the basic substance is at least one of calcium carbonate and calcium hydroxide, and the neutral substance is zinc oxide. Deodorizing film.

9. A breathable deodorizing film characterized in that activated clay and a basic substance or a neutral substance and a neutral substance are kneaded with a polyolefin resin, then melted and formed into a film, and the film is stretched. Production method.

10. The method for producing a breathable deodorized film according to claim 9, wherein the activated clay has an acidity of 10 to 30 m.e. 100 g and a specific surface area of 150 to 300 m ² / g.

II. The claim 9 or 10 wherein the basic substance is at least one of calcium carbonate and calcium hydroxide, and the neutral substance is zinc oxide. For producing a breathable deodorizing film.