JP2849754B2 - Method for producing bactericidal acrylic fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a low-cost acrylic fiber having permanent sterilization useful in the fields of clothing, interiors, and industrial materials.

[Conventional technology]

Hitherto, silver and copper have been known to exhibit excellent bactericidal properties, and various methods have been disclosed for imparting permanent bactericidal properties to acrylic fibers using the properties of this bactericidal metal.

That is, an acrylic fiber containing 0.6 to 1.0 mol% of a sulfonic acid group-containing vinyl compound as a copolymer component is treated with a copper salt or silver salt-containing aqueous solution, and the acrylic fiber contains at least 0.1 meq / g fiber. A method of binding copper ions or silver ions (Japanese Patent Laid-Open No. 52-92000), heat treatment of an acrylic fiber in an aqueous solution containing monovalent copper ions, and conversion of monovalent copper to nitrile groups in the fibers. After adsorption
A method of treating with a reducing agent to precipitate metallic copper in the fiber (Japanese Patent Application Laid-Open No. 55-51873), a method of adsorbing monovalent copper to a nitrile group in an acrylic fiber, followed by a treatment with a sulfur-containing compound. , A method of incorporating copper sulfide into fibers (Japanese Patent Laid-Open No. 56-1283)
No. 11).

[Problems to be solved by the invention]

As described above, the prior art relating to imparting bactericidal properties to acrylic fibers utilizing the properties of bactericidal metals is a post-processing technique of the fibers. The post-processing technology of the fiber generally has a problem that a processing step is complicated, productivity is low, and a product cost is high.

An object of the present invention is to solve the problems of the technique for imparting sterilization properties to acrylic fibers by post-processing as described above, and to provide a low-cost method for producing sterilizable acrylic fibers.

[Means for solving the problem]

The present invention relates to a method for producing a germicidal acrylic fiber, which comprises spinning, drawing, and heat-treating a spinning stock solution obtained by dissolving acidic group-containing acrylonitrile-based resin fine particles to which a bactericidal metal ion is bound in a solvent. is there.

The acidic group-containing acrylonitrile-based resin fine particles used in the present invention can be used directly as the acidic group-containing acrylonitrile-based copolymer fine particles used in the production of ordinary acrylic fibers or modacrylic fibers. Various vinyl monomers that copolymerize with acrylonitrile, such as methyl acrylate, methyl methacrylate, vinyl acetate, vinyl chloride, vinylidene chloride, and other second components, and allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, and acrylic A third copolymer component such as an acid and methacrylic acid may be included as a copolymer component.

In the present invention, as the acrylonitrile resin containing an acidic group, an acrylonitrile copolymer containing an acidic group at the terminal of a polymer derived from a polymerization system, or an acrylonitrile resin obtained by copolymerizing an acidic group-containing vinyl monomer. Either a binary or terpolymer can be used, and the amount of acidic groups in the acrylonitrile resin fine particles is about 50%.
If it is at least mmol / kg, an effective amount of metal ions can be bound, and excellent permanent sterilization can be imparted.

As a method for producing the acrylonitrile-based resin fine particles containing an acidic group formed by binding the ions of the bactericidal metal of the present invention, a method of treating the acrylonitrile-based resin fine particles containing an acidic group in an aqueous solution containing a bactericidal metal ion is preferably used. Can be

Silver, copper and zinc are preferably used as the germicidal metal of the present invention, and silver is particularly preferably used in view of the bactericidal effect of the fiber and whiteness.

As the metal ion-containing aqueous solution, an aqueous solution of a metal salt is used. Examples of the metal salt include salts such as nitric acid and acetic acid, but nitrates are preferably used industrially. The acrylonitrile-based resin fine particles are immersed in an aqueous solution of a metal salt, and the concentration of the metal salt in the aqueous solution when the metal ion is bonded to the acidic group in the resin fine particles is equimolar to the amount of the acidic group in the acrylonitrile-based resin fine particles to be immersed. Preferably, the concentration is lower than that.

When an aqueous solution having a concentration equal to or less than the amount of the acidic group in the acrylonitrile-based resin fine particles is used, the metal ion can be almost bound to the acidic group in the resin fine particles, which is industrially advantageous.

On the other hand, the bonding rate of metal ions to acidic groups in the acrylonitrile-based resin fine particles is greatly affected by the fine structure of the resin fine particles.

That is, since the undried acrylonitrile-based resin fine particles of the water-based polymerization degree have a relaxed structure, the bonding rate of metal ions is extremely fast, whereas, after the water-based polymerization, the dried resin fine particles have a dense fine structure. Therefore, the bonding speed of metal ions is reduced.

Accordingly, when acrylonitrile-based resin fine particles to which metal ions are bonded are industrially produced, a method using undried acrylonitrile-based resin fine particles after aqueous polymerization is preferably used.

When the acrylonitrile-based resin fine particles after the aqueous polymerization are immersed in a metal ion-containing aqueous solution, the treatment temperature is preferably 80 to 100 ° C., and the treatment time is preferably several minutes to several tens of minutes.

After binding the metal ions to the acrylonitrile-based resin fine particles, they are sufficiently washed with water and dried to provide a spinning dope.

The spinning solution is prepared by dissolving acidic group-containing acrylonitrile-based resin particles formed by bonding metal ions using an organic solvent such as dimethylformamide or dimethylacetamide in the same manner as in a normal spinning solution for acrylic fiber production. Thus, the spinning solution can be adjusted.

In the present invention, an acidic group-containing acrylonitrile-based resin fine particles having metal ions bonded thereto and ordinary acrylonitrile-based resin fine particles having no metal ions bonded thereto are mixed at an appropriate ratio, and this is dissolved in an organic solvent. It can be a spinning solution.

The method for producing the fiber using the adjusted spinning solution can be a conventional method for producing an acrylic fiber as it is, and may be any of a wet spinning method, a semi-wet spinning method, and a dry spinning method.

In addition, as a spinning method using a spinning dope, in addition to a single spinning method using a single spinning dope, a composite spinning method with another spinning dope can also be used.

Spinning, stretching, and the like during the production of the sterilizable acrylic fiber of the present invention.
Heat treatment conditions can be used as normal acrylic fiber production conditions as they are, without any need for process improvement, making it possible to produce low-cost sterilizable acrylic fibers with ordinary acrylic fiber production equipment. Is what you do.

〔The invention's effect〕

The germicidal acrylic fiber of the present invention is similar to a normal fiber,
It can be spun and knitted, can be processed into various forms depending on the application, and can supply inexpensive textile products for clothing, interior, and industrial materials that require sterilization. Yes, its industrial effect is extremely large.

〔Example〕

Hereinafter, the content of the present invention will be described in more detail with reference to examples. The bactericidal property and the durability of the bactericidal property described in the text were measured by the following methods.

(1) Measurement of bactericidal activity Place the test fibers of 1 cm length in a 1 cm width on an agar medium inoculated with Staphylococcus aureus, incubate the bacteria at 37 ° C for 24 hours. The presence or absence of bactericidal activity was determined based on the growth of bacteria.

(Bactericidal property) ：: No growth of bacteria is observed around the sample, and halo is generated.

Δ: No bacterial growth was observed around the sample, and no halo was generated.

×: Bacterial growth is observed around the sample.

(2) Measurement of sterility durability After the test fiber was subjected to durability treatment under the following conditions, the sterility was measured to determine the presence or absence of sterility durability.

Laundry treatment Using a home washing machine, New Beads (Kao Soap Co., Ltd.
After washing for 5 minutes in a washing liquid at 40 ° C. containing 2 g / neutral detergent), washing treatment with running water for 1 minute is repeated 10 times, followed by centrifugal dehydration and drying.

Dyeing treatment Using a money type dyeing machine, an aqueous solution containing 1% owf (based on fiber weight) of Catilon Blue GLH (manufactured by Hodogaya Chemical Co., Ltd.), 1% owf of acetic acid and 0.5% owf of sodium acetate was used. : After staining at 50,98 ° C for 45 minutes, wash with water, centrifugally dehydrate and dry.

Example 1 Acrylonitrile-based resin fine particles comprising 93% by weight of acrylonitrile and 7% by weight of vinyl acetate and having an acidic group content of 50mmol / kg polymer after water-based polymerization were mixed with 0.04% by weight of silver nitrate.
Immersed in an aqueous solution containing
After being treated at 98 ° C. for 10 minutes with stirring, it was sufficiently washed with water and dried to obtain acrylonitrile-based resin fine particles having an average particle diameter of about 50 μm and bound with silver ions.

The resin fine particles were dissolved using dimethylacetamide to prepare a spinning dope having a resin concentration of 23% by weight.

The undiluted spinning solution was discharged into a dimethylacetamide-water-based coagulation bath at 40 ° C., stretched 5 times in hot water at 98 ° C., washed with water, treated with an oil agent, dried at a fixed length using a hot roller, and then dried.
A heat shrink treatment was performed in saturated steam at 8 ° C. for 30 minutes to obtain a silver-containing acrylic fiber.

Table 1 shows the results of measuring the single fiber performance and the sterilization property of this fiber.

Example 2 30 parts by weight of acrylonitrile-based resin fine particles to which silver ions were ion-bonded and acrylonitrile 93 used in Example 1 were used.
Acrylonitrile-based resin fine particles of 70% by weight and not bound with silver ions composed of 70% by weight of vinyl acetate and 7% by weight of vinyl acetate are mixed and dissolved with dimethylacetamide to obtain a resin concentration
A spinning stock solution of 23% by weight was prepared.

This spinning solution was spun, drawn, and heat-treated in the same manner as in Example 1 to obtain a silver-containing acrylic fiber.

Table 1 shows the results of measuring the single fiber performance and the sterilization property of this fiber.

Comparative Example Aqueous-polymerized acrylonitrile-based resin fine particles of 93% by weight of acrylonitrile and 7% by weight of vinyl acetate and having an acidic group content of 50 mmol / kg polymer used in Example 1 were sufficiently washed with water, dried, and dried. Acrylonitrile-based resin fine particles having a diameter of about 50 μm were obtained.

The resin fine particles were prepared in the same manner as in Example 1 to prepare a spinning solution, and then spun, drawn and heat-treated to obtain acrylic fibers.

Table 1 shows the results of measuring the single fiber performance and the sterilization property of this fiber.

From the above results, the single fiber performance of the germicidal acrylic fiber of the present invention shows a value equivalent to that of the normal acrylic fiber shown in the comparative example, and almost no decrease in the single fiber performance due to imparting bactericidal property is recognized.

In addition, it can be seen that the bactericidal acrylic fiber of the present invention exhibits excellent permanent bactericidal properties and excellent bactericidal properties even after repeated washing and dyeing.

Continuation of the front page (56) References JP-A-54-38951 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) D01F 6/18 D01F 1/10

Claims (2)

(57) [Claims] 1. A method of producing a sterilizing acrylic fiber, comprising spinning, drawing and heat-treating a spinning stock solution obtained by dissolving an acrylonitrile-based resin fine particle containing an acidic group, to which ions of a sterilizing metal are bonded, in a solvent. Method. 2. The method according to claim 1, wherein the germicidal metal is at least one selected from the group consisting of silver, copper and zinc.