JPH01111068A - Production of deodorizing fiber - Google Patents

Abstract

PURPOSE: To obtain a deodorizing fiber having an excellent deodorizing performance over a long period by impregnating a thermoplastic synthetic fiber with the aqueous solution of a polyalkylene glycol-based compound containing a metal porphyrazine compound and subsequently thermally treating the treated fiber at a specific temperature. CONSTITUTION: This deodorizing fiber is obtained by impregnating a thermoplastic synthetic fiber with the water-mixed solution (weight mixing ratio: 3/7 to 9/1) of a polyalkylene glycol (mol.wt: <=1,000)-based compound containing >=0.3 wt.% of a metal porphyrazine compound [preferably a compound of the composition (X is H, carboxy, sulfonic acid or metal salt or amino, provided that at least one of X groups is carboxy, sulfonic acid or metal salt; Me is divalent trivalent iron ion or cobalt ion)] and subsequently thermally treating the treated fiber at a temperature of 100-200 deg.C. Thereby, the deodorizing fiber to which the excellent characteristics of the thermoplastic synthetic fiber and further the excellent stink-decomposing function are uniformly added is obtained.

Description

[Detailed Description of the Invention] Industrial Field of Application The present invention can be used as a filler, a filter, or in various other ways to eliminate odors in places where bad odors are generated, such as in cars, chestnuts, toilets, and hospital rooms. The present invention relates to a method for producing deodorizing fibers.

BACKGROUND ART Conventionally, there are the following methods for removing bad odors.

(1) Mask the odor with a substance that has a strong odor.

(4) Fixing bad odors such as ammonia and hydrogen sulfide with metal salts such as zinc sulfate.

(Ill) Neutralize and make odorless.

(1φ activated carbon adsorbs bad odors.

However, the effects obtained by the above means are not permanent, and the effects fade over time, and the drug must be replaced or regenerated as appropriate.

Furthermore, when activated carbon is used, its adsorption capacity varies depending on temperature and humidity, and there is a drawback that it re-releases the odor components that have been adsorbed.

As a means to eliminate the above-mentioned drawbacks, by using a deodorizing agent isolated from plants of the Camellia family in combination with a hydrophilic compound, it is possible to use a deodorizing agent isolated from plants of the Camellia family in combination, without damaging the texture of the fibers, even in high humidity environments where odors are likely to occur. It has been disclosed that a deodorizing filler having a deodorizing effect can be obtained (Japanese Patent Publication No. 22978/1983).

However, even with the above method, since the fiber surface is simply coated, there are problems with the durability of the effect and the fastness to washing.

On the other hand, in recent years, deodorizing fibers that have semi-permanent deodorizing properties have been developed, which are made by adsorbing metal porphyrazines to porous rayon or wool. The metal porphyrazines are different from normal adsorption and masking in that they decompose ammonia, mercaptan, etc. and change them into odorless substances, and are therefore thought to exhibit semipermanent deodorizing properties. ing.

Problems to be Solved by the Invention As mentioned above, metal porphyrazines have semi-permanent deodorizing properties, but when applied to fibers, they do not have uneven surfaces like porous rayon or wool. However, it is difficult to adsorb to fibers with a smooth surface and small contact area, such as synthetic fibers such as polyamide and polyester, and they tend to fall off during use and have low washing fastness. There is a point.

The present invention solves the above-mentioned problems when imparting deodorizing properties to thermoplastic synthetic fibers such as polyamide and polyester using metal porphyrazines as deodorants. The object of the present invention is to provide a method for producing deodorizing fibers that uses metal porphyrazines to impart effective deodorizing properties over a long period of time.

Means for Solving the Problems In order to solve the above-mentioned problems, the method for producing deodorizing fibers of the present invention includes adding polyalkylene glycosylated polyalkylene glycosylation containing 0.3 weight or more of metal porphyrazine to thermoplastic synthetic fibers. - impregnated with ρ-based compound-water mixed solvent solution, then 100°C ~
It is characterized by heat treatment at a temperature of 200°C.

Examples of the thermoplastic synthetic fiber used in the present invention include synthetic fibers such as polyamide, polyester μ, and polypropylene. As polyamide fibers, in addition to nylon 6 and nylon 66 fibers, copolymer fibers are used, and as polyester μ fibers, in addition to polyethylene phthalate and polybutylene phthalate fibers, acid components such as adipic acid, sepacic acid, azephinic acid, Isophthalic acid, 5-sodium hoisophthalic acid, alcohol component:
A polymer obtained by copolymerizing a small amount of each of 1-4 butanediol, 1-6 hexanediol, neopentyl glycol, etc. can also be used. The form of fibers is filament,
It may be short fibers, woven fabrics, knitted fabrics, etc. In the case of filaments, it is preferable that the winding form can be heat treated, whether it is undrawn yarn, drawn yarn, or false twisted yarn. It may also be a fiber bundle in the process.

Margin below Metal porphyrazines are represented by the following formula.

At least one is a carboxy μ group or a metal salt thereof or a sulfonic acid group or a metal salt thereof, and Mdd is a divalent or trivalent iron ion or a divalent or trivalent cobalt ion. ) A mixed solution of a polyalkylene glycol compound and water is used as the solvent for the porphyrazine. Other solvents are unsuitable because they have disadvantages such as poor solubility of metal porphyrazine, poor ability to adhere metal porphyrazine to fibers, and easy to cause uneven adhesion. As a polyalkylene glyco-μ type compound, the molecular weight is 1
Polyethylene glyco-μ of 000 or less, polypropylene glycol, and copolymers, esterified products, and etherified products thereof are suitable. When the molecular weight exceeds 1,000, some substances become solid at room temperature, and there are disadvantages such as difficulty in dissolving or requiring a long time to dissolve when mixed with water, and the swelling ability for fibers is also reduced. It is not preferable due to the following problems, and it is desirable to have a molecular weight of 500 or less. The mixing ratio (weight) of polyalkylene glycol and water is preferably in the range of 3/7 to 9/1,
In a range other than the above, the solubility of the metal porphyrazine, the treatment effect, etc. tend to decrease.

The concentration of the metal porphyrazine polyalkylene glycol compound-water mixed solvent solution must be at least 0.3 weight range, and if it is less than 0.3 weight range, the fibers will retain sufficient deodorizing properties. Therefore, the required amount of adhesion cannot be obtained.

A solution of the metal porphyrazine can be easily prepared by heating a mixed solvent of a kylene glycol compound and water to 40°C to 60°C, adding the metal porphyrazine, and dissolving it while stirring. can be obtained.

The metal porphyrazine is added to the thermoplastic synthetic fiber as follows. First, after removing oils, finishing agents, etc. adhering to the surface of the fibers, the fibers are immersed in a mixed solvent solution of a metal porphyrazine, polyalkylene glycol compound, and water at a predetermined concentration. Solution temperature is 50°~70°
A temperature of about C is preferable for removing air bubbles on the fiber surface and increasing the treatment effect. Although the reason is not clear, when a weakly acidic substance such as formic acid or acetic acid is added to the solution to adjust the pH to below -7, the adhesion of the metal porphyrazine to the fibers becomes better. However, lowering the pH below 3 is not preferable because it may cause problems such as corrosion of the processing container.

Next, the fibers immersed in the solution are taken out, and after squeezing, the fibers are heat-treated in the air at a temperature of 100 to 200° C. in a wet state. The heat treatment is preferably carried out until the polyalkylene glycol compound and water adhering to the fibers are evaporated or decomposed and volatilized. Heat treatment temperature is 100℃
At low temperatures, the adhesion of metal porphyrazines to fibers is weak, so most of them fall off when washed with water, and
If the temperature is higher than 00℃, the metal porphyrazine will thermally decompose and the deodorizing property will decrease.
It is necessary to carry out the test at 00°C.

Effect In the above configuration, when attaching metal porphyrazines to thermoplastic synthetic fibers, a polyalkylene glyco/L/based compound-water mixed solvent having a swelling effect on thermoplastic synthetic fibers is used as a solvent for metal porphyrazines. By using the solution, the permeability into the inside of the fiber becomes good, and by impregnating the fiber with the metal porphyrazine solution and then heat-treating it at 100'C to 200'C, The solvent is allowed to penetrate into the interior of the T-type fibers, and the solvent is evaporated, decomposed and volatilized, so that the solvent can be firmly and evenly adhered to the fibers, and fibers with long-lasting and excellent deodorizing properties can be obtained.

Examples Example 1 Processed yarns of polyethylene terephthalate and nylon 6, each having a 150 denier fiJ/48 filament, were knitted into tubes, washed with water, and then dried at 105° C. for 30 minutes. −° side A mixed solution of tetraethylene glycol μ and water was prepared at a tetraethylene glycol/water mixing ratio of 8/2.7/'3.5/15.
The mixed solution was heated to 50°C, and a metal bolus of phthalocyanine octacarboxylic acid was added, and in the combinations shown in Table 1,
Create a solution with a concentration of 0.5, L5, Z5% by weight,
Acetic acid was added to adjust the pHt to 3.5, 6.0, and 6.5.

Next, the above-mentioned polyethylene terephthalate-processed yarn tube knitted fabric and nylon 6-processed yarn tube knitted fabric were washed and dried in combination as shown in Table 1, and added to the above iron (1) phthalocyanine octacarboxylic acid solution at 60°C. The fibers were immersed in water for 1 minute, stirred, and taken out of the solution, and the 11 J solution was removed to obtain a solution adhesion amount of about 3 times the weight of the fibers.

Heat treated in a hot air dryer for 20 minutes at 150°C and 180°C, then washed with water, and then heated at 80°C under a reduced pressure of 100 Torr for 30 minutes.
Dry for 0 minutes. From the pre-treatment dry weight WO and post-treatment dry weight W of the tubular knitted fabric, the adhesion amount of iron (button phthalocyanine octacarboxylic acid (weight 4>t) was calculated using the following formula.

W　-W.

Amount of adhesion (regret) = WoX 100 The mixing ratio of the above solvent, solution concentration, solution PH, heat treatment temperature, amount of adhesion, and unevenness of adhesion are summarized in Table 1.

As a comparative example, the same treatment as in the above example was carried out using tetraethylene glyco-μ and water as solvents. Table 1 shows the conditions, amount of adhesion, and unevenness of adhesion.

The following margin * Uneven adhesion: O... No uneven adhesion, ×... Uneven adhesion As is clear from the results shown in Table 1, the tubular knitted fabric obtained in the above example contains iron (1). A large amount of phthalocyanine octacarboxylic acid was adhered evenly.

The deodorizing properties of the iron (1) phthalocyanine octacarboxylic acid-adhered tubular knitted fabrics and untreated tubular li fabrics obtained in the above Examples and Comparative Examples were measured by the following method.

■ 300M! Pour 8 of the 2NH40H solution into a triangular fusco
．． 8wt1, and 2g' of the above tube knitted fabric test piece in it.
After hanging and covering with a lid to prevent the rNH40H solution from adhering, it was left in a room at 25°C, and after 2 hours, 8 hours, and 24 hours.
After a period of time, the concentration of NH in the gas in the Erlenmeyer flask was measured using a gastic detection tube (manufactured by Iuchi Seieido).

This is the initial addition.

(2) After measuring the concentration after 24 hours in (2) above, 8.8 gt of 2N NH40H solution was added again, and the NH concentration was measured again after 24 hours had elapsed.

(2) Repeat the above operation (2) in which the 2N NH40H solution was added again three times (total of four times). The above items ① and ② are re-added.

The deodorizing properties were measured using the above method and the results are shown in Table 2.

As is clear from the results shown in Table 2, the tubular knitted fabric obtained in the above example has significantly better performance in decomposing ammonia gas than the comparative example, and has an extremely good deodorizing effect over a long period of time. showed his sexuality.

Example 2 The solvent for iron phthalocyanine octacarboxylic acid was mixed with polyethylene glycol having a molecular weight of 500 and water at a mixing ratio of 5.
Except for changing the mixture to A, everything was the same as in Example 1 above.
(Table 1) A yarn tube knitted fabric treated with deodorizing polyethylene terephthalate was obtained by processing under the same conditions as the sample. The amount of adhesion, uneven adhesion, and deodorizing performance were measured in the same manner as in Example 1. The results are shown in Table 3.

Example 3 The same procedure as in Example 1 was repeated, except that the solvent for iron (1) phthalocyanine octacarboxylic acid was changed to a mixture of polyethylene glyco-fi/(molecule fk200) dilauryl ester and water at a mixing ratio of 515. (Table 1) A yarn tube knitted fabric treated with deodorizing polyethylene terephthalate was obtained by processing under the same conditions as the sample. The amount of adhesion, uneven adhesion, and deodorizing performance were measured in the same manner as in Example 1. The results are shown in Table 3.

As is clear from the results shown in Table 3, the tubular knitted fabrics obtained in Example 2 and Example 3 both had iron phthalocyanine carboxylic acid adhered in large amounts and evenly, and were excellent. It had excellent ammonia gas decomposition performance and exhibited extremely good deodorizing properties over a long period of time.

Effects of the Invention As described above, by attaching metal porphyrazines to thermoplastic synthetic fibers such as polyamide and polyester, in addition to the excellent properties of these thermoplastic synthetic fibers, the present invention has an excellent odor decomposition function. can be applied evenly and extremely easily, and the obtained fibers exhibit excellent deodorizing performance over a long period of time.
It can be used in various forms such as rugs, filters, etc. to exhibit extremely excellent deodorizing effects.

Agent Hiroshi Mori Moto

Claims (1)

[Claims] 1. 0.0% metal porphyrazine is added to the thermoplastic synthetic fiber.
Impregnated with a polyalkylene glycol compound-water mixed solvent solution containing 3% by weight or more, and then heated at 100°C to 20°C.
A method for producing deodorizing fibers, characterized by heat treatment at a temperature of 0°C. 2. The method for producing deodorant fibers according to claim 1, wherein the metal porphyrazine is a compound represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X is hydrogen, a carboxyl group or its metal salt, a sulfonic acid group or its metal salt, or an amino group, and at least one is a carboxyl group or its metal salt. salt or sulfonic acid group or its metal salt, and Me is a divalent or trivalent iron ion or a divalent or trivalent cobalt ion.) 3. The polyalkylene glycol compound-water mixed solvent is The method for producing deodorant fibers according to claim 1, wherein the alkylene glycol compound has a molecular weight of 1000 or less, and the polyalkylene glycol compound/water mixing ratio (weight) is from 3/7 to 9/1. . 4. The method for producing deodorant fibers according to claim 1, wherein the pH of the metal porphyrazine solution is adjusted to 3 to 7.