JPS626953A - Deodorizing nonwoven fabric - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a deodorizing nonwoven fabric, and more particularly to a deodorizing needling nonwoven fabric suitable for filters and mats for removing bad odors.

[Conventional technology]

As is well known, adsorbent substances 1 such as activated carbon, acid clay, diatomaceous earth, or activated alumina are commonly used in various filters for the purpose of deodorization (Japanese Patent Laid-Open No. 53-47
(See Publication No. 89).

In addition, since metal porphyrin in general, and copper chlorophyllin in particular, has remarkable deodorizing properties, it is also possible to make deodorizing sheet materials for filters and the like by applying a polymer containing a porphyrin-like compound with a metal coordinated at the center. This is known (see Japanese Patent Laid-Open No. 133590/1983).

[Problem that the invention seeks to solve]

However, in a nonwoven fabric made by mixing and supporting the adsorbent substance in a fiber material as described above, the surface area occupied by the adsorbent substance relative to the entire nonwoven fabric is limited, and it cannot be expected to maintain the deodorizing effect for a long period of time. In addition, the adsorbent substance is binder fiber,
For example, since the thermal adhesive fibers are bonded and supported to the fiber material by thermal melting, the actual adsorption surface area of the adsorbent substance is further reduced.

Filters coated with polymers containing metal porphyrin have the advantage of providing a long-term deodorizing effect compared to filters that combine adsorbent substances, and are particularly effective against hydrogen sulfide, mercaptans, etc. Demonstrates removal action. However, since deodorant polymers are added to filters through an application method, when liquid malodors, such as animal excrement, are passed through, the deodorant polymers are dissolved and separated by the flow of liquid, and then The problem arises that the deodorizing function of the deodorizing function rapidly decreases. Moreover, it is extremely difficult to apply this technique to heavy materials such as needled nonwoven fabrics.

The present invention has excellent deodorizing ability against all kinds of bad odors such as hydrogen sulfide, mercaptans, ammonia, and amines, and has a long-lasting deodorizing ability with almost no deterioration in deodorizing ability due to liquid flow. The present invention provides a needling non-woven fabric that is compatible.

[Means for solving problems]

A first invention for solving problem 1 is a fiber in which at least a part of the constituent fibers contains 1% by weight or more of a metal complex having redox ability, and 0.1% by weight of metal ions.
This is a deodorizing nonwoven fabric that is needle-punched and is made of m-fibers that have the following properties:

Similarly, in a second invention, at least a part of the configuration tam,
This is a deodorizing nonwoven fabric that is needle-punched and is made of fibers that support 1% by weight or more of a metal complex having redox ability and 0.1% by weight or more of metal ions.

As the metal complex, which is a deodorizing component supported on the fibers, metal porphyrins, metal porphyrazines, and derivatives thereof, which have redox ability, are used. , are chemically bonded and supported to form a polymer metal complex. Metalloporphyrin and its derivatives are represented by the structural formula shown in FIG.

Metal porphyrazine is represented by the structural formula shown in FIG. In both formulas, for example, Fe, Co, Mn,
Examples include metal ions such as Ti, V, Ni, Cu, Zn, No, and W. Among these metal ions, iron and cobalt are preferred from the viewpoint of deodorizing effect. In both formulas, X represents hydrogen or a substituent. Examples of substituents include alkyl groups, substituted alkyl groups (e.g. chloromethyl group), halogen groups, nitro groups, amino groups, azo groups, thiocyanate groups, carboxyl groups, carbonyl chloride groups, carboxylamide groups, nitrile groups, hydroxyl groups, alkoxyl group,
Phenoxydyl group, sulfonic acid group, sulfonyl chloride group, sulfonamide group, thiol group, alkyl silicon group,
In addition to vinyl groups, examples include alkali salts of carboxyl groups and sulfonic acid groups. These may be used alone or in combination of two or more. Among these, carboxyl groups, sulfonic acid groups, alkali salts thereof, amine groups, halogen groups, hydroxyl groups, and the like are preferably used.

The most preferred examples of the JL form of the metal complex having redox ability are cobalt phthalocyanine octacarboxylic acid, cobalt phthalocyanine tetracarboxylic acid, iron phthalocyanine octacarboxylic acid, and iron phthalocyanine tetracarboxylic acid.

The above metal complexes may be used alone or in combination of two or more.

The required amount of metal complex supported varies depending on the type of metal complex, but is generally 1% by weight or more -L. The larger the amount, the more deodorizing activity will be obtained; if the amount is smaller, the desired level of deodorizing activity will not be obtained, and the sustainability of the deodorizing activity will also be poor. However, there is a limit to the amount that the fiber can support the metal complex, and the preferred amount is in the range of 1 to 20% of heavy acid.

The metal ions that are the deodorizing component incorporated into the fibers are transition metal ions, such as copper, iron, cobalt, and nickel, but metal ions other than transition metals include calcium,
Barium and magnesium are good. The metal ions to be supported may be used alone or in combination of two or more.

Then, metal ion 11! It is preferable that the amount supported be as large as possible, but from the viewpoint of economy and the strength and shape retention of the supported fibers, about 0.1 to 20% by weight is appropriate. The above-mentioned metal ions may be held in direct physical contact with the fibers, or may be chemically bonded to and supported on the polymers of the fibers. In the latter example, a polymeric metal complex is formed of an intramolecular chelate complex of polyvinyl alcohol and copper ions, a complex of polyvinylamine and iron ions, etc. Further, the compound containing the metal ion may be carried by physically contacting the fiber, or may be carried by being chemically bonded to the polymer of the fiber.

Examples of fibers supporting metal complexes and fibers supporting metal ions include regenerated cellulose fibers, hygroscopic synthetic fibers, porous fibers, and porous hollow fibers.
Particularly preferred are regenerated cellulose fibers, immature cotton, or acetate rayon having a degree of secondary swelling of 150 to 500%.

[Effect]

Due to the action of the metal complex having redox ability which is supported by the fibers constituting the nonwoven fabric of the present invention, malodorous substances such as hydrogen sulfide and mercaptans are oxidized and decomposed and rendered odorless. That is, the metal coordinated with the porphyrin and porphyrazine rings serves as an active center, and the oxidation reaction proceeds.

For example, taking the oxidation of mercaptan as an example, the oxidation is shown by the following chemical reaction formula.

2R-3H+ 20H-→2R-8-+21120. ．．
=-(1)2R-8-+ 2)120+ 02→R-9
-8-R+ H2O2+ 2011-4. (2) (1)
The thiolate anion produced in the reaction of the formula coordinates with oxygen to porphyrin and porphyrazine to form an active species that is a ternary complex. The thiolate anion coordinating with this active species is converted into a disulfide shown by the formula (2) via a thiyl radical, and is incorporated into the fiber to become odorless.

In the case of hydrogen sulfide, it decomposes into odorless sulfur and water as shown in the following formula.

2H2S + 02 → 2S + 2H20 This reaction is very similar to in vivo enzymatic oxidation reactions. All oxidation reactions by enzymes are aerobic reactions. In other words, most of them undergo oxygen oxidation reactions. Examples of oxidation reactions of odor-like substances by oxidizing enzymes include those shown in the following table.

Enzyme reaction system Reaction Example H2SO3+H20+02→H2SO4+ H2O2 Oxygenase type Cleavage of double bond Cleavage of indole nucleus As shown above, oxidation (deodorization) of mercaptan compounds, sulfonation (water solubilization, deodorization), quinone of phenolic compounds (deodorization) and cleavage of the indole nuclear double bond (deodorization). The oxidation reaction by metal complexes proceeds in the presence of a small amount of moisture at room temperature, and the reaction rate is fast and the reaction rate is high.

Further, odor substances made of ammonia or various amine compounds have a more effective deodorizing effect due to the metal ions that are supported on the fibers. That is, the metal ions supported on the fibers form a metal ammine complex in the presence of ammonia and various amines and moisture. For example, the reaction in which ammonia is adsorbed to copper ions to form a complex is a reaction in which a complex is exchanged between water molecules of Eiwa copper ions and floating ammonia molecules, as shown by the following equation.

[Cu(OH2)I42◆+4HH3+ [Cu(N
H3) 412++4H20 This complex exchange reaction has a fast reaction rate and a very high reaction rate, and the formed metal ammine complex is also adsorbed very stably.

〔Example〕

Example 1. (First, title of the invention - Highly swellable rayon staples with a blowing swelling rate of about 200%, a length of 51 m/m, and a thickness of 5 denier were prepared using an aqueous solution of iron phthalocyanine polycarboxylic acid (aqueous solution concentration 3 gel).
After being immersed in a solution (pH 12), the fibers were dehydrated and dried to obtain fibers (hereinafter referred to as fiber A) carrying about 2% by weight of iron phthalocyanine polycarboxylic acid.

- On the other hand, the same highly swellable rayon staple as above was immersed in an aqueous copper acetate solution (concentration 5 g/l), then dehydrated and dried to carry about 2.5% by weight of copper acetate (hereinafter referred to as fiber B). Obtained. The above A fiber web (500 g/m2) was superimposed on the B fiber web (500 g/mQ) via a coarse base fabric made of hemp fiber yarn, and needle punching was performed using a conventional method (punch density: 70 pieces/cm2). A non-woven fabric with an apparent thickness of about 10 m+a was obtained.This non-woven fabric was cut into a square of 20 cm+o x 20 cm to make a filter material.

Example 2. (Example of the first invention) A fiber web (500 g/m2) obtained by mixing the A fibers and B fibers of Example 1 with this acid was coated with a length of 51 m through a coarse base fabric.
/a, polypropylene fiber webs (200 g/m2) with a thickness of 4 denier were superimposed and needle punched in the same manner as in Example 1 to obtain a nonwoven fabric with an apparent thickness of about 8 m/m. This non-woven fabric is 20c+aX 20cm
Cut into square pieces to make filter material.

Example 3. (Example of the second invention) The A fiber of Example 1 above is immersed in an aqueous copper acetate solution (concentration 5 g/4) and then dehydrated and dried. As a result, approximately 2 μ% iron phthalocyanine polycarboxylic acid and approximately 2.541% copper acetate
A supported fiber was obtained.

Co (1) mfm know ) were piled up and subjected to needle punching using a conventional method to obtain a nonwoven fabric with an apparent thickness of about 8H. This nonwoven fabric is cut into a 20cm x 20cm+ square to make a filter material.

Example 4. (Example of the second invention) A fiber web (500 g/m2) containing about 2% by weight of the iron phthalocyanine polycarboxylic acid obtained in Example 3 above and about 2.5% of copper acetate was coated with a coarse base. length 5 through cloth
Polypropylene am webs (200 g/1rr2) with a thickness of 1 m/m and a thickness of 4 denier were overlapped and needle-punched in the same manner as in Example 1 to an apparent thickness of about 8 m.
/m of nonwoven fabric was obtained. This non-woven fabric is 20cm x 20
Cut into c+o squares to make filter material.

The filter materials of Examples 1 to 4 above were installed in the deodorizing test apparatus shown in FIGS. 3 and 4 to examine their performance.

In the apparatus shown in FIG. 3, a fixed amount of foul-smelling gas is sent from an inlet 1 per hour, and the gas, which has passed through a conduit 2 and passed through a filter 3, is subjected to a sensory test at an outlet 4. Filter 3
The filter material obtained in the above example is stacked on three sheets, and the water faucet 5 is
Test each piece one by one while keeping it moist by continuously supplying a small amount of water. When hydrogen sulfide gas with a concentration of 500 PPM was fed at a rate of 200 cc/min, almost no hydrogen sulfide odor was felt. Furthermore, as a result of a continuous test, there was no odor at all even after 40 hours had passed. When the malodorous gas was changed to 60 PPM of ammonia gas, IPPM of methyl mercaptan, and IPPM of trimethyl meramine, good results were obtained.

The device shown in Figure 4 has the ability to deodorize complex malodorous substances such as cow manure, pig manure, chicken manure, raw deep bed, deep bed treatment plant cake, fish pulp, sewage sludge, and sewage treatment plant cake. It is to be tested. A glass bottle containing 10 complex malodorous substances
When air is pumped through the pump 12, a compound odor is generated. The compound malodorous gas passed through the filter 3 and was stored in a pack 14 for trace analysis. For the filter 3, three sheets of the filter material obtained in the above example are stacked one on top of the other, and a very small amount of water is continuously supplied from the faucet 5 to keep the filter in a moist state, and each piece is tested one by one.

The results were as shown in the table below.

(Margins below) Note: The complex odor source was measured using a gas detection method after anaerobic fermentation at 37°C for 100 hours. However, some of the sewage treatment plant cakes were fermented by blowing air from time to time (this seal). In the table, (−
) indicates that it could not be measured using the gas detection method. The average odor intensity of the monitor is 1, which is the intensity of the odor that you can smell even though you don't know what it is.For example, if 1 out of 5 people felt the odor, it is 0. It was displayed as .2.

In each of the above examples, the fibers are made to carry metal complexes and metal ions having redox ability, which are deodorizing ingredients, and then punched to make a nonwoven fabric. Deodorizing ingredients can be combined.

〔Effect of the invention〕

As explained below, the deodorizing nonwoven fabric to which the present invention is applied has the ability to oxidize and decompose malodorous components through a reaction similar to that of biological oxidases of metal complexes supported on fibers, as well as to decompose malodorous components from metal ions supported on fibers. It is based on a metal amine complex formation reaction, and has a large deodorizing effect that lasts for a long time. Since its shape is a nonwoven fabric, it can be applied to a wide range of fields, such as deodorizing filters, deodorizing mats, and various deodorizing core materials.

[Brief explanation of drawings]

Figure 1 is a diagram showing the structural formula of metal porphyrin, Figure 2 is a diagram showing the structural formula of metal porphyrazine, and Figures 3 and 4 are schematic configuration diagrams of a deodorizing test apparatus for deodorizing nonwoven fabric. . l...Inlet port 2... Conduit 3...
・ Filter 4-...Exhaust 11511. Water faucet
10. ,,. Complex malodorous substance 11, glass bottle 12. ,,,,Pump 14,,,,,Pack

Claims (1)

[Scope of Claims] 1. At least a part of the constituent fibers is composed of fibers carrying 1% by weight or more of a metal complex having redox ability and fibers carrying 0.1% by weight or more of metal ions. A deodorizing nonwoven fabric characterized by being needle-punched. 2. Constructed of fibers in which at least a portion of the constituent fibers supports 1% by weight or more of a metal complex having redox ability and 0.1% by weight or more of metal ions, and is needle-punched. Characteristic deodorizing nonwoven fabric. 3. The metal complex having redox ability is iron phthalocyanine polycarboxylic acid or cobalt phthalocyanine polycarboxylic acid.
The deodorizing nonwoven fabric according to claim 1 or 2, characterized in that it is a polycarboxylic acid. 4. The deodorizing nonwoven fabric according to claim 1 or 2, wherein the metal of the metal ion is copper, cobalt, or iron.