JP2002105852A - Method for modifying synthetic fiber and synthetic resin with sulfur trioxde in vapor-phase - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for imparting various functions to synthetic fibers or synthetic resins. SOLUTION: The synthetic fibers or synthetic resin in brought into contact with sulfur trioxide gas and then washed with a wash liquid comprising water or an aqueous solution of an alkali metal salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for modifying synthetic fibers and synthetic resins using sulfur trioxide (sulfuric anhydride) gas.

[0002]

2. Description of the Related Art The following is a conventional modification method which is carried out to make a synthetic fiber functional. 1. The method of imparting water absorbency makes use of the capillary phenomenon skillfully. Fine fibers and irregular cross-section fibers are appropriately gathered in a woven or knitted fabric to form capillaries at appropriate intervals to allow water to be absorbed. 2. The antistatic method is a chemical method of imparting hydrophilicity by attaching a surfactant to which water is adsorbed, or a physical method of kneading a highly conductive metal in the fiber. 3. The method for imparting flame resistance is to knead the flame retardant at the raw material stage or to fix the flame retardant to the fibers by post-treatment. 4. In the deodorizing method, a metal having an antibacterial action is contained in ceramics having fine pores, and it is kneaded into fibers. 5. The easy dyeing method produces a modified polyester having improved dyeability and texture by introducing a sulfone group at the monomer stage and copolymerizing the polyester.

[0003] As described above, in order to impart various functions to synthetic fibers, a method of kneading a chemical at the raw material stage or a method of performing a special processing at the time of spinning is often used. There are few things by post-processing after becoming. In addition, as a conventional post-processing, there is a weight-reduction processing of polyester fabric in which sodium hydroxide and a weight-reducing agent are used in combination, and the processing is performed by heating, but this method requires a large amount of chemicals and a long processing time. There is a disadvantage that.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and its object is to provide a synthetic fiber or synthetic resin with various functionalities by a reaction with sulfur trioxide gas and a subsequent post-treatment. It is another object of the present invention to provide a reforming method for imparting the following. Among them are new weight loss processing methods which replace the weight loss processing method of polyester using sodium hydroxide. The synthetic fibers or synthetic resins to be modified here include polyolefin polymers such as polyester, polyamide, polyimide, polyethylene or polypropylene, and vinyl polymers such as acrylonitrile or vinyl chloride.

[0005]

In order to achieve the above object, the present invention employs a method in which sulfur trioxide is brought into contact with a synthetic fiber or a synthetic resin by a gas, followed by washing with water or alkali or alkali metal salt. Is performed with an aqueous solution of This means can introduce various functions by introducing a sulfone group or a sulfonate group into the surface of the synthetic fiber or synthetic resin. 1. When the gas-phase sulfur trioxide treatment is performed, sulfone groups are introduced, and water absorption and hygroscopicity can be imparted. As a result, the fibers themselves have a moisture retention property, and the chargeability is reduced. Further, the sulfone group adsorbs ammonia and amines, and the adsorbability of malodorous substances is improved. 2. Washing with an aqueous solution of an alkali metal salt (such as sodium carbonate) after gas-phase sulfur trioxide treatment results in the fiber surface being covered with a sulfonate group, reducing water charge and moisture while maintaining water absorption and hygroscopicity. Can be. When a silver salt such as silver nitrate is introduced into the alkali metal salt, antibacterial property can be expected. 3. After the gas phase sulfur trioxide treatment, if the substrate is washed with an ammonia treatment or an aqueous ammonia solution, the fiber surface is covered with a sulfamine group, so that flame resistance is imparted. 4. If the polyester treated with the sulfur trioxide gas is washed with water or an aqueous alkali solution, the polyester weight reduction processing is performed easily and in a short time, which leads to simplification of the process as compared with the conventional weight reduction processing. Note that this weight loss is due to ester hydrolysis by sulfurous acid by-produced in the reaction and sulfuric acid by-produced with a small amount of water in addition to the sulfonation described above.

The method of the present invention is different from the conventional methods in which each is independently processed, and has a desired function by selecting a treatment after contacting a synthetic fiber or a synthetic resin with a sulfur trioxide gas. There is a feature to make it.

The sulfur trioxide gas acts on the surface of the synthetic fiber or synthetic resin to introduce a sulfone group, so that the moisture absorption and water absorption of the single fiber itself are improved, and as a result, the charged voltage is reduced. In addition, it is possible to impart deodorant properties by a sulfone group, antibacterial properties by introducing a silver salt, flame resistance by introducing a sulfamine group, and antibacterial properties by introducing a silver salt. And the texture can be improved by the effect of the weight reduction processing.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The method for modifying a synthetic fiber or synthetic resin according to the present invention comprises a step of contacting sulfur trioxide gas and a subsequent washing step. Next, the process will be described.

(Sulfur trioxide gas contacting step) A sulfone group is introduced into the surface of the synthetic fiber / synthetic resin by bringing the sulfur fiber trioxide gas into contact with raw cotton, woven fabric or synthetic resin. Examples of the object to be treated in the present invention include synthetic fiber raw cotton, woven fabric, and synthetic resin products.

In the embodiment of the present invention, a process for polyester will be described as a representative of the object to be processed.
The sulfur trioxide gas to be brought into contact with the polyester is diluted with an inert gas such as nitrogen, argon, helium or the like or dry air, but nitrogen gas or dry air is preferred in terms of cost. The dilution of sulfur trioxide gas is 0.5% by volume.
%, The reaction is insufficient, and there is no difference in the reaction even at 5.0% or more. Therefore, the content of nitrogen gas or dry air is 99.5% by volume or less, preferably 95.0 to 99.5% by volume. %.

The temperature at which sulfur trioxide is brought into contact is 29
If the temperature is lower than 3 K (20 ° C.), the vaporization rate of solid or liquid sulfur trioxide is low, so the temperature is set to 293 K (20 ° C.) or more, preferably 318 to 323 K (45 to 50 ° C.). If the contact time is less than 0.1 minute, the reaction is insufficient, and even if it is 20 minutes or more, there is no difference, so the contact time is set to 0.1 to 20 minutes, preferably 1 to 10 minutes.

The reactor is not particularly limited. The reactor is previously replaced with dry air. The polyester sample may be fixedly or continuously supplied into a reactor replaced with dry air, and nitrogen gas or sulfur trioxide gas diluted with dry air may be introduced into the reactor and brought into contact therewith.

The contacting step of the sulfur trioxide gas with the polyester in the present invention is a gas phase reaction, so that the gaseous treating agent is easily diffused into the inside of the aggregate of the objects to be treated, and uniform treatment is performed. The sulfur trioxide gas and by-product sulfur dioxide used in the present invention are discharged from the reactor,
Since it is recovered in concentrated sulfuric acid or neutralized with an alkaline solution, it does not cause environmental pollution or environmental destruction.

(Washing step) Next, the polyester sample brought into contact with the sulfur trioxide gas is taken out batchwise or continuously and washed with water to reduce the surface weight and simultaneously remove sulfurous acid and sulfuric acid present on the surface. Can be removed. Further, by washing with an aqueous solution of an alkali or an alkali salt, sulfonate groups can be introduced to the surface.

As the aqueous solution of an alkali salt used for washing, an aqueous solution of an alkali metal carbonate, hydrogen carbonate, hydroxide or the like, for example, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, An aqueous solution such as potassium hydroxide may be used. Further, a silver salt or the like is introduced into the alkali metal salt for washing. As the alkali, cleaning is performed with ammonia or an aqueous ammonia solution. By selecting the type of the washing method, a desired modification is applied to the synthetic fiber and the synthetic resin.

The washing method includes washing by stirring, washing by jetting, and washing by ultrasonic waves.

In the conventional method for reducing the weight of alkali, the treatment is carried out at a high temperature using sodium hydroxide and a reducing agent, which requires a large amount of energy and time. However, the weight loss processing of the method of the present invention is performed by the gas phase treatment of sulfur trioxide, which also causes the polyester surface to be disintegrated at the time of imparting functionality, so that the heat energy is reduced as compared with the conventional method. It saves energy and reduces the chemicals and time required for processing. Disintegration of the polyester surface is also caused by hydrolysis of the ester main chain by sulfurous acid and sulfuric acid by-produced during the sulfur trioxide treatment.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described based on embodiments. After treating the polyester sample with sulfur trioxide, Example 1 was washed with water, Example 2 was washed with a sodium hydroxide solution, and Example 3 was washed with an aqueous ammonia solution.

Example 1 6 g of a polyester sample was fixed in a reaction vessel, the inside of the apparatus was evacuated, and the inside of the vessel was replaced with dry nitrogen gas. At this time, the entire apparatus is warmed to 318 K (45 ° C.). Next, it is charged into the apparatus so that the concentration of sulfur trioxide becomes 1.1% by volume, and vaporized. 10 samples and sulfur trioxide gas
The treatment was carried out by contacting for 1 minute. In the same procedure, the treatment was performed while changing the treatment concentration to 2.2 and 3.3% by volume. After treatment, after washing with water, 338K (6
5 ° C).

Example 2 A polyester sample treated in accordance with Example 1 was treated with 0.1%
After washing with a 05N sodium hydroxide solution, it was dried at 338 K (65 ° C.) under normal pressure.

Example 3 A polyester sample subjected to a reaction treatment according to Example 1
After washing with a 5% aqueous ammonia solution, it was dried at 338 K (65 ° C.) under normal pressure.

The following functional tests were performed on the treated and untreated polyester samples of each of the examples.

1. Hygroscopicity and hydrophilic performance test Hygroscopicity and hydrophilic performance test of the polyester samples obtained in Examples 1 and 2 were performed by the following method.

Hygroscopicity: The polyester samples obtained in Examples 1 and 2 were dried at 378 K (105 ° C.) for 4 hours, and the absolute dry weight was measured. Next, the sample was heated to a temperature of 293K (2
(0 ° C.) and a humidity of 60% in a constant temperature room for 4 hours, and then the weight was measured to determine the moisture absorption.

Hydrophilicity: Distilled water was dropped on the polyester samples obtained in Examples 1 and 2, and the time for which the shape of the water droplet was maintained was measured. The results are as shown in Table 1. The polyester samples of Examples 1 and 2 have higher hygroscopicity than the untreated polyester sample and are excellent in hydrophilic performance.

[0026]

[Table 1]

2. Weight loss rate test The weight loss rate of the polyester samples obtained in Examples 1 and 2,
The following method was used. The sample weight before the gas phase trioxidation treatment and the weight after the treatment were measured, and evaluated based on the change in weight. As a measurement sample, a sample dried at 338 K (65 ° C.) under normal pressure was used. The measurement results are as shown in Table 2, and the polyester samples of Examples 1 and 2 are reduced in weight according to the reaction gas concentration.

[0028]

[Table 2]

3. Charge-charge performance test The charge-charge performance of the polyester samples obtained in Examples 1 and 2 was measured by a rotary charge measurement method at 293 K (20 ° C.) and a humidity of 40%. The measurement results are as shown in Table 3, and the charged voltages of the polyester samples of Examples 1 and 2 are lower than that of the untreated polyester sample. Example 2
With respect to (2), since a part of the polyester component sulfonated during the alkali post-treatment is dissolved in the washing solution, the charging voltage tends to decrease when the concentration of sulfur trioxide increases.

[0030]

[Table 3]

4. Deodorizing performance test The deodorizing performance of the polyester sample obtained in Example 1 was performed by the following method. Deodorization test: A sample after sulfur trioxide treatment was placed in an odor bag, a predetermined amount of ammonia gas was injected, and the residual ammonia amount after 30 minutes was measured. The measurement results are as shown in Table 4, and the residual ammonia amount of the polyester sample of Example 1 is significantly lower than that of the untreated polyester sample.

[0032]

[Table 4]

5. Dyeability test The dyeability of the polyester sample obtained in Example 1 was measured by the following method. Dyeing property: Ni as cationic dye
chilon Blue PR 200% (CIIB
asic 41) 0.5% o. w. f and dyed and evaluated by colorimetry. The results are as shown in Table 5. The dyeability of the polyester sample of Example 1 is much better than that of the untreated polyester sample.

[0034]

[Table 5]

6. Flameproofing performance test The flameproofing performance of the polyester sample obtained in Example 3 was measured by the following method. Flame resistance: After heating for 5 seconds based on the vertical method, evaluation was made based on the carbonization distance and the afterflame time. The results are as shown in Table 5 (related standard: JIS L1091.1.
3) The polyester sample of Example 3 is more excellent in flame resistance than the untreated polyester sample.

[0036]

[Table 6]

[0037]

As described above, the method of the present invention improves the hygroscopicity of a synthetic fiber / synthetic resin by introducing a sulfone group / sulfonate / sulfamine group into the surface of the synthetic fiber / synthetic resin, It has an excellent effect of imparting functions such as deodorant, flameproof, dyeing, and antibacterial properties.

Further, the present invention as a weight reduction processing method has a remarkable effect that it contributes to energy saving because the required heat energy load, chemical consumption and processing time are reduced as compared with the conventional alkali weight reduction processing. .

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Claims (5)

[Claims] A synthetic fiber or a synthetic resin is brought into contact with sulfur trioxide gas, and then water or an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, calcium hydroxide, aqueous ammonia, or sodium carbonate, potassium carbonate,
A method for modifying synthetic fibers and synthetic resins by gas phase sulfur trioxide treatment, comprising washing with a washing solution comprising an aqueous solution of an alkali metal salt such as sodium hydrogen carbonate and potassium hydrogen carbonate. 2. A method for modifying synthetic fibers and synthetic resin by gas-phase sulfur trioxide treatment, comprising bringing synthetic fibers or synthetic resin into contact with sulfur trioxide gas and then treating with ammonia gas. 3. A method for modifying synthetic fiber and synthetic resin by gas phase sulfur trioxide treatment, comprising contacting synthetic fiber or synthetic resin with sulfur trioxide gas, and then treating with a silver salt aqueous solution. 4. The sulfur trioxide gas contains nitrogen gas or dry air at 99.5% by volume or less, preferably 95.0 to 99.5%.
The method for modifying synthetic fibers and synthetic resins by a gas-phase sulfur trioxide treatment according to any one of claims 1 to 3, wherein the synthetic fiber and the synthetic resin are contained by volume%. 5. The temperature at which the synthetic fiber or synthetic resin is brought into contact with the sulfur trioxide gas is 293 K (20 ° C.) or more, preferably 318 to 323 K (45 to 50 ° C.), and the contact time is 0.1.
The method for modifying synthetic fibers and synthetic resins by gas-phase sulfur trioxide treatment according to any one of claims 1 to 4, wherein the treatment is performed for 1 to 20 minutes, preferably 1 to 10 minutes.