JPH02157040A - Fibrous deodorant - Google Patents

Abstract

PURPOSE:To provide a powerful and lasting fibrous deodorant by selecting the substances having a specific property as adsorbent and dispersion stabilizer and causing thermoplastic high-molecular compound to contain the adsorbent at a high rate. CONSTITUTION:An adsorbent for use for a fibrous deodorant, undecomposable at a temperature of not more than 150 deg.C, contains metallic oxide, metal hydroxide and metal carbonate, e.g. tungsten oxide and zinc hydroxide, and is added thereto a dispersion stabilizer, e.g. silane coupling and polyethylene imine, capable of diffusing homogeneously a thermoplastic high-molecule compound and the adsorbent. This can increase the adsorbent content of the fiber material by 20 - 50wt.%. Previously added to the deodorant material in this way, the adsorbent will not be desorbed from the deodorant producing a powerful and lasting effect.

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a deodorizing agent in which an adsorbent for adsorbing odors is mixed into a fiber raw material in advance, and this is spun to form a fiber, which can maintain high deodorizing efficiency over a long period of time. provide something. <Prior art> The fibrous deodorizer that is the object of the present invention basically comprises a fiber raw material mainly composed of a thermoplastic polymer compound having fiber-forming ability and an adsorbent, and the fiber raw material is The conventional technology for this fibrous deodorizer, which can be obtained by integrally kneading and melt-spinning, includes (1) ferrous sulfate and ferrous nitrate, as shown in Japanese Patent Application Laid-Open No. 62-22331.8. , iron salts of inorganic acids such as ferrous chloride, or (2) iron compounds such as iron salts of organic acids such as iron lactate, iron acetate, and iron gluconate into thermoplastic polymers such as polybutylene ethylene phthalate. After dispersing, the iron compound is contained in a range of 0.3 to 5.0% by weight as iron metal,
There is a product in which a thermoplastic polymer containing an iron compound is mixed with polyester and spun. Generally, as shown in Japanese Patent Application Laid-Open No. 58-159752, cloth-like deodorizers in which an adsorbent such as activated alumina is fixed to the surface of a cloth are weak in durability because the adsorbent falls off during washing, etc. While the deodorizing effect is not long lasting, the fabric woven from the above-mentioned fibrous deodorizing agent has good washing fastness and the deodorizing effect lasts for a long time. <Problems to be Solved by the Invention> However, in the above-mentioned prior art, the iron compound as an adsorbent is contained in the fibrous deodorizer only in a small amount of 0.3 to 5.0% by weight as iron metal. The reality is that the time it takes for the adsorbent to reach a saturated state after the odor is adsorbed is short, and the deodorizing effect is not great, and there is a risk that the deodorizing effect will decrease if used for a long period of time. The technical objective of the present invention is to provide a fibrous deodorizing agent with a strong and permanent deodorizing effect. <Means for Solving the Problems> The present inventors have focused on the fact that by selecting specific substances for the adsorbent and dispersion stabilizer, it is possible to fill a thermoplastic polymer compound with a high content of adsorbent. , completed the invention. Accordingly, the present invention provides that, in the basic structure of the fibrous deodorizing agent, the adsorbent is undecomposed at least below 150'C, and contains metal oxides, metal hydroxides, metal carbonates, and metal phosphorus. The fiber raw material contains at least one kind of acid salt, metal inorganic acid salt, metal organic acid salt, metal silicate, etc., and a dispersion stabilizer is mixed into the fiber raw material, and the content of the adsorbent to the fiber raw material is 20 to 5.
It is characterized by being 0% by weight. The above metal oxides include tungsten oxide, nickel oxide,
Zinc oxide, titanium oxide, molybdenum oxide, iron oxide, magnesium oxide, manganese oxide, vanadium oxide, lead oxide,
Refers to chromium oxide, copper oxide, and cobalt oxide. The metal hydroxides mentioned above refer to zinc hydroxide, iron hydroxide, calcium hydroxide, and magnesium hydroxide. The metal carbonates include nickel carbonate, zinc carbonate, magnesium carbonate, calcium carbonate, lead carbonate, potassium carbonate, copper carbonate, barium carbonate, mankan carbonate, and the like. The metal phosphate mentioned above refers to zinc phosphate, chromium phosphate, cobalt phosphate, magnesium phosphate, and the like. The above-mentioned metal inorganic acid salts refer to metal sulfates such as ferrous sulfate and zinc sulfate. The above-mentioned metal organic acid salts refer to zinc acetate, zinc acetate, zinc lactate, and the like. The metal silicates mentioned above include pure substances such as sodium silicate, hentonite, kaolin, talc, zeolite,
Natural materials such as activated clay, natural loess, and silica gel (or
synthetic) refers to porous mineral materials. As the adsorbent, a mixture of several kinds of metal compounds of the substances listed in 1 is preferable, but these are not decomposed at least below 150° C. and can exhibit a deodorizing effect even under high temperature conditions. Further, the deodorizing effect can be reinforced by impregnating the spun fibrous deodorizing agent with a liquid adsorbent. '' Bipedal liquid adsorbents include ■Aliphatic and aromatic aldehydes such as cinnamic aldehyde and dodecyl aldehyde; ■Organic acids and their salts such as ascorbic acid, tartaric acid, and zinc tartrate; ■Stearyl trimethyl ammonium chloride;
Cationic and hyanionic surfactants such as polyoxyethylene-alkyl phenyl ether sodium sulfate, ■Betaine, ■Aliphatic and aromatic esters such as lauryl methacrylate and methyl benzoate, ■From plants such as bamboo extract, etc. Examples include extracts of Is a dispersion stabilizer mixed into the above fiber raw material in order to uniformly disperse the thermoplastic polymer compound and adsorbent, and is the dispersion stabilizer such as a silane coupling agent or a titanium coupling agent? , these are added with polyethyleneimine (P
It is more preferable to add a polymer flocculant such as EI) or polyacrylamide (FAA), which is advantageous in increasing the adsorbent content relative to the fiber raw material. If the content of the adsorbent to the fiber raw material is too low, the deodorizing efficiency will decrease, and if it is too high, the mechanical strength of the fiber will decrease.
0% by weight is more preferred. The thermoplastic polymer compound is not particularly limited as long as it has a fiber-forming ability, including polypropylene, polyester, nylon, polyethylene, polyacrylonitrile, etc., but polypropylene, polyester, and nylon are more preferred. <Function> Since the content of the adsorbent to the fiber raw material is 20 to 50% by weight, when extruding the fiber raw material from a spinneret and spinning it,
Fibrous deodorizers can maintain appropriate mechanical strength. The fibrous deodorizer has the following characteristics: (1) The adsorbent content is extremely high, at 20% by weight or more; (2) Due to the spinning process, there are cracks and depressions on the surface and the surface area is large, and a large amount of the surface is Since the adsorbent is exposed in the area, it is extremely active and has a high adsorption reaction rate against malodorous gases or malodorous liquids, and has a very high deodorizing ability. Further, when the fibrous deodorizing agent is subjected to stretching treatment, the cracks and depressions on the surface are increased, and the deodorizing ability is further enhanced. <Effects of the Invention> The adsorbent is mixed into the fiber raw material in advance and then spun, so it does not fall off from the deodorizer, so this deodorizer has extremely high washing fastness and has a high adsorbent content. Depending on the rate and spinning process, the deodorizing efficiency can be strong and permanent. <Example> Hereinafter, a production example of the fibrous deodorizing agent of the present invention will be described, and the results of an experiment on deodorizing a predetermined odor scum using the fibrous deodorizing agent will be shown.

[Example 1] 53 g of silane coupling agent (dispersion stabilizer) was diluted with methanol (solvent N0 kg), and 4 kg of adsorbent prepared at the following ratio was immersed in this methanol solution. The agent was impregnated with a 7-run coupling agent. Adsorbent composition: Zinc oxide 5Qwt% Activated clay 20wt% Iron sulfate 20wt% 50g of PEI (dispersion stabilizer) was diluted with methanol, and the above treated solution was added to the methanol solution. The adsorbent was further impregnated with PEr while the solvent was blown off. Using a speed mixer, polyethylene terephthalate +
-(p E T) 2.5 g of zinc stearate (crystallizing agent) was added to 5 kg of resin and kneaded, then the above adsorbent was added and kneaded, and then dioctyl phthalate h (DOP:
10 g of plasticizer) was added and sufficiently kneaded to obtain a premix. Next, 5 kg of the above premix and 5 kg of PET resin were further kneaded in a speed mixer to prepare a fiber raw material. Then, the fiber raw material described in 1 was melt-spun using an extrusion molding machine under the following conditions to obtain a polyester-based fibrous deodorizer (in this case, the adsorbent content was approximately 22%).
. Spinning temperature 260-280℃ Discharge amount per single hole of spinneret] kg/min,
hole spinning speed・2Qm/min

[Example 2] 53 g of silane coupling agent was diluted with 10 kg of methanol, 4.4.5 kg of adsorbent prepared at the following ratio was immersed in this methanol solution, and the silane cup was added to the adsorbent while evaporating the solvent by heating. Impregnated with ring agent. Adsorbent composition Nickel carbonate 25wt% natural loess
5Qwt% activated clay
Using a 25wt% speed mixer, add 2.5g of zinc stearate and 50g of FAA (dispersion stabilizer) to 5kg of polyamide resin and knead, then add and knead the above adsorbent, and further add DOPl and Og, A premix was obtained by thorough kneading. Next, 5 kg of the above premix and 4 kg of polyamide resin were mixed, and the subsequent steps were carried out in the same manner as in Example 1 to produce a nylon-based fibrous deodorizer. However, in this case, the adsorbent content in the deodorizer is approximately 26
%Met.

[Example 3] 45 g of titanium coupling agent (dispersion stabilizer) was diluted with 4.5 kg of toluene (solvent), 4.5 kg of adsorbent prepared at the following ratio was immersed in this toluene solution, and heated. While removing the solvent, the adsorbent was impregnated with a titanium coupling agent. Composition of adsorbent Nickel carbonate 45wt% Natural Ceolite h 45wt% Zinc oxide IQwt% Add 2.5g of zinc stearate to 5kg of polypropylene (PP) resin and knead using a speed mixer, then add and knead the above adsorbent, Furthermore, DOP30g
was added and sufficiently kneaded to obtain a premix. Next, 5 kg of the premix described in "1" and 5 kg of PP resin were mixed, and the subsequent steps were carried out in the same manner as in Example 1 to produce a polypropylene-based fibrous deodorizing agent. However, the adsorbent content in the deodorizer was approximately 24%.

[Example 4] A 2% by weight aqueous solution of bamboo extract containing 5% by weight of ethylene glycol was used as a liquid adsorbent in the above Example 1.
A fibrous deodorizer was soaked in this aqueous solution for 5 minutes,
After removing excess water, dry with hot air at 60'C.
The fibrous deodorizer was impregnated with a liquid adsorbent. In this case, the liquid adsorbent has a very strong interaction with the solid adsorbent contained in the fibrous deodorizing agent, and is difficult to peel off even by washing with water.

[Experiment example of deodorizing performance]

Each of the fibrous deodorizers obtained in Examples 1 to 4 above was applied to the experimental apparatus shown in FIG. We conducted experiments for comparison purposes. That is, 7.0 g of fibrous deodorizer (3) was placed in a petri dish (2).
This was placed on the bottom of a 20C polyethylene tank (1). Then, three types of foul-smelling gases, ammonia, hydrogen sulfide, and methyl mercaptan, are blown into the tank (1) from the two-part inlet (4) on the left wall of the tank (1) to bring the inside of the tank to a predetermined concentration.
Changes in the concentration of each residue over time in the tank were measured using a gas concentration measuring device (gas chromatography, commercially available gas detector, etc.) (5) attached to the right side wall. However, the initial concentration of each malodorous gas is as follows,
Performance comparisons of deodorizers were made using the following residual ratios. Initial concentration of ammonia: 1100 ppm Initial concentration of hydrogen sulfide: 50 ppm Initial concentration of methyl mercaptan 50 ppm Residual ratio - Ct/C. Ct: gas concentration after a predetermined time Co/initial residue concentration Figures 2 to 4 are graphs showing the deodorizing effect on each malodorous gas. The residual ratio of methyl mercaptan is 50% or more, and in particular, it is approximately 80% for methyl mercaptan, which indicates that it does not have much deodorizing effect. On the other hand, in Examples 1 to 4, the residual ratio was 0% after 48 hours, and in particular, it can be seen that Example 4 impregnated with a liquid adsorbent has the best deodorizing performance ( The residual ratio of ammonia and hydrogen sulfide reached 0% after 6 hours, and the residual ratio of methyl mercaptan reached 0% after 24 hours.) As mentioned above, the present invention is characterized by a fibrous deodorizing agent in which a high content of adsorbent is mixed into fiber raw materials in advance, and this is melt-spun. Can be formed into (2) By mixing the short fibers of the deodorizing agent with Hinter, heating and welding, it can be formed into a non-woven fabric. (3) This short fiber can be formed into paper by dispersing it in water, mixing it with pulp if necessary, and drying it with or without adding inter. Therefore, woven fabrics, non-woven fabrics, paper, etc. processed with the above-mentioned fibrous deodorizers can be used as filters for various air conditioners and air purifiers,
It can be used for wallpaper, calendars, bed sheets, futons, cushions, food packaging materials, etc. In addition, it can be used in a wide range of fields, including deodorizing agents for places where bad odors are likely to occur, such as deodorizing agents for toilets and refrigerators, and deodorizing agents for lockers and chests of drawers.

[Brief explanation of the drawing]

Fig. 1 is a schematic explanatory diagram of an experimental apparatus for testing the deodorizing performance of the fibrous deodorizing agent of the present invention, Fig. 2 is a graph showing the deodorizing results of ammonia, Fig. 3 is a graph showing the deodorizing results of hydrogen sulfide, and Fig. 4 is a graph showing the deodorizing results of hydrogen sulfide. The figure is a graph showing the deodorization results of methyl mercaptan. 1.Tank, 2.Nyare, 3.Fibrous deodorizer, 4.
At the inlet of the tank, 5. Residue concentration measuring device. Patent applicant Azumi Filter Paper Co., Ltd. Nippon Kasei Co., Ltd.

Claims (1)

[Claims] 1. A fiber raw material is composed of a thermoplastic polymer compound having fiber-forming ability and an adsorbent as the main components, and the fiber raw material is kneaded and melt-spun together to form a deodorizing agent with the adsorbent fixed thereon in the form of fibers. In the fibrous deodorizing agent, the adsorbent is undecomposed at least below 150°C, and is a metal oxide, metal hydroxide, metal carbonate, metal phosphate, metal inorganic acid salt, metal organic acid salt. , a metal silicate, etc., a dispersion stabilizer is mixed into the fiber raw material, and the content of the adsorbent with respect to the fiber raw material is 20 to 50% by weight. .