JPH02229209A - Antimicrobial acrylic synthetic fiber and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject fiber excellent in antimicrobial properties and fastness to washing by dispersing a fine particulate metal oxide having the surface coated with an antimicrobial metal in an organic solvent, adding the dispersion to a solution of an acrylonitrile-based copolymer in an organic solvent and wet spinning the resultant solution. CONSTITUTION:The objective fiber, obtained by homogeneously dispersing a metal oxide having the surface, coated with a metal (e.g. silver, copper or zinc) and having antimicrobial properties and 0.1-5mu, preferably 0.3-2mu average particle diameter in an organic solvent (e.g. DMF), adding and mixing the resultant dispersion with a solution of an acrylonitrile-based copolymer in an organic solvent and then wet spinning the prepared solution and containing 0.1-10wt.%, preferably 0.3-5.0wt.% above-mentioned metal oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an acrylic synthetic fiber having excellent anti-cotton effect and a method for producing the same. (Prior art) Acrylic synthetic fibers are widely used for clothing and bedding interiors, but in recent years there has been a strong demand for antibacterial and anti-mold properties, which are often used in cloaks and carpets used in the nursery field. It's coming.

Conventionally, methods have been known in which natural or synthetic fibers are coated or coated with a compound that has antibacterial and antifungal properties, or the fibers are impregnated with a solution of the compound, but such methods do not have long-lasting effects. The disadvantage is that the applied chemicals are easily washed away by washing or the like. Furthermore, the method of resin processing using chemicals and resin to impart washing resistance to fibers has the disadvantage of impairing the texture of the fibers.

Up to now, copolymers containing acrylonitrile have been combined with copper compounds or fine metal powders of copper and zinc (Japanese Patent Laid-Open No. 55-115440).
No. 2, etc.), or a method of adding and spinning an azole derivative (
JP-A No. 53-139895) has been proposed, but it is difficult to obtain a good dispersion state and the fibers aggregate, resulting in poor spinnability and the contact area for bacteria is small, making it antibacterial. It had the disadvantage of being insufficiently effective. Additionally, azole derivatives have problems with toxicity, which hinders their practical application.

The present inventors completed the present invention as a result of intensive research to improve the above drawbacks. (Problems to be Solved by the Invention) An object of the present invention is to provide an acrylic synthetic fiber having excellent antibacterial and antifungal properties that has washing resistance and can be applied to a wide range of fiber processing conditions. Still another object is to provide a method for manufacturing such antibacterial acrylic synthetic fibers industrially easily and at low cost.

(Means for Solving the Problems) The antibacterial acrylic synthetic fiber of the present invention contains a metal oxide whose surface is coated with a metal having antibacterial properties.
The presence of 10% by weight is considered a vf signature.

In addition, in the method of the present invention, when manufacturing acrylic synthetic fibers by wet spinning, metal oxides having an average particle size of 0.1 to 5μ and whose surface is coated with a metal having antibacterial properties are uniformly dispersed in an organic solvent. This is then added to an organic solvent solution of the acrylonitrile copolymer, and then spun.

The acrylonitrile copolymer component used in the present invention has at least 40% by weight of acrylonitrile as a constituent monomer, and preferably has fiber-forming ability.
stomach. That is, 40% by weight or more of acrylonitrile and other monomers such as acrylic acid. methacrylic acid,
These alkyl esters are vinyl acetate. Vinyl chloride vinylidene chloride. Sodium allylsulfonate 5 Sodium methallylsulfonate, sodium vinylsulfonate, sodium styrene sulfonate, sodium 2-acrylamide 2-methylpropanesulfonate, etc. 60
Examples include those copolymerized in a proportion of less than % by weight.

In particular, a copolymer of 80% by weight or more of acrylonitrile and 20% or less of a vinyl heptanomer and a sulfonic acid group-containing monomer, or a copolymer of 40% by weight or more of acrylonitrile and 20 to 20% of vinylidene chloride and a sulfonic acid group-containing monomer. 6
A copolymer containing 0% by weight is preferred.

Examples of metals having antibacterial properties used in the present invention include silver, copper, zinc, etc., and the metal oxide particles are surface coated in an amount of 1 to 20% by weight, preferably 3 to IO weight%.

If the amount of coating is less than 1.0%, sufficient antibacterial performance cannot be imparted unless the amount of metal oxide added to the acrylonitrile copolymer is increased, or spinnability and spinnability in spinning may deteriorate. descend. Moreover, if it exceeds 20% by weight, the surface coating layer becomes thick, making it difficult to manufacture at a low cost, and furthermore, coloring when made into textile products becomes a problem. The amount of the metal oxide whose surface is coated with an antibacterial metal depends on the type of metal and the amount of surface coating, but it is 0 to 0 to the acrylic copolymer.
．． 1-10% by weight, preferably 0.3-5.0% by weight
Contain. If it is less than 0.1% by weight, sufficient antibacterial properties cannot be imparted to the fibers, and if it exceeds 10% by weight, the fiber performance will decrease and the spinnability and spinnability in spinning will decrease. Further, the particle size is usually 5 μm or less, preferably 0.5 μm or less. 3~
It is 2 μm. When the particle size exceeds 5 μm, the spinnability in spinning and the performance of the obtained fibers deteriorate. The solvent used in the method of the invention is dimethylformamide. Dimethylacetamide. Dimethyl sulfoxide. Examples include known organic solvents used for spinning acrylic synthetic fibers, such as acetone.

Any known wet grinder can be used as the dispersion device, but in order to continuously add the dispersion liquid to the spinning dope, a sand grinder, pearl mill, or grain mill may be used. A flow tube type crusher such as Dyno Mill is suitable.

In the present invention, a metal oxide whose surface is coated with a metal having antibacterial properties is used. The dispersion concentration of the fI agent solution is usually 5 to 40% by weight, preferably 15 to 30% by weight.
It is. If this concentration is less than 5% by weight, the concentration of the spinning stock solution decreases, and the spinnability and fiber properties decrease, although it depends on the amount of metal oxide added. Moreover, if it exceeds 40% by weight, a good uniform dispersion state cannot be obtained and it becomes difficult to easily produce it industrially. Spinning can be carried out under the same conditions as ordinary acrylic synthetic fibers, including passing through several baths, sequentially drawing, and washing with water. Perform drying and post-processing.

(Effects of the Invention) The antibacterial acrylic synthetic fiber of the present invention has an excellent antibacterial effect, has the same fiber performance as ordinary acrylic synthetic fiber, and has excellent washing resistance. There is also almost no decline in anti-drying effect evaluated by try-cleaning resistance. Further, the manufacturing method of the present invention allows such fibers to be manufactured industrially easily and at low cost using the manufacturing conditions and equipment/equipment for ordinary acrylic synthetic fibers.

The fibers obtained according to the present invention can be used in combination with other fibers such as ordinary acrylic synthetic fibers, polyester, nylon, cotton, rayon, wool, etc., and can be used in clothing, blankets, and other materials with antibacterial properties. It is extremely meaningful industrially because it can be used for a wide range of purposes such as beds, mattresses, socks, sheets, futon cotton, etc.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. still,
In the examples, "%" means "weight %j."

Examples 1 to 4 and Comparative Examples 1 to 3 Acrylonitrile (AN)/methyl acrylate} (M
A)/Sodium methacryl sulfonate (SMAS) = 9
A dimethylformamide (DMF) solution of an acrylic polymer consisting of 1.2/8.0/0.8 was prepared.

Then, titanium dioxide (average particle size 1.0 μm) whose surface was coated with a metal having resistance to the acrylic copolymer in the amount listed in Table 1 was divided into DMF in a homomixer, and then the acrylic copolymer It was added to the copolymer solution and thoroughly stirred with a homomixer to obtain a spinning stock solution. The above stock solution was heated to 20°C and 60% DM. F water? After stretching and washing with water while spinning in solution '8 and removing the medium, an oil agent was applied and drying and densification were performed. After crimping this fiber,
Heat treatment was performed at 120°C. The resulting fibers were canted and spun to produce circular knits.

This knitted fabric is l. It was cut into pieces of 5 g (approximately 3 to 5 cm square cloth) and subjected to an antibacterial test.

On the other hand, as a comparative example, an acrylonitrile copolymer was added in an amount different from the amount described above.

[Antibacterial test conditions]

Knitting 1. Cut into 5 g pieces, add Staphylococcus aureus or Klebsiella pneumoniae buffer, shake in a sealed container at 150 times/min for 1 hour, count the number of viable bacteria, and calculate the number of bacteria in the injected suspension. The rate of decrease was calculated. The spinning operability is evaluated in four stages: "◎", "rOJ, r△", and "×" based on the filtration pressure, single yarn breakage, roller I cut, etc. when manufactured under the conditions described in the examples. evaluated.

Further, the degree of coloring was visually judged in four stages.

As is clear from Table 1, the Example products have superior antibacterial performance compared to the Comparative Example products.

Example 6 DMFf! of an acrylic copolymer consisting of 8N/vinylidene chloride (VCj!t)/sodium allylsulfonate (SAS) = 57/'40/3! I prepared iJ solution. The acrylic copolymer was treated with 1.0% titanium dioxide with a surface coating of 5% silver, uniformly dispersed by a sand grinder, and then added to the acrylic copolymer solution and thoroughly stirred. It was used as a spinning stock solution. The above spinning stock solution was heated at 25°C.
, was spun into a 55% DMF aqueous solution, stretched and washed with water while removing the solvent, and then dried and densified by applying an oil agent. After crimping this fiber, it was heat-treated at 115°C.

The obtained fibers were made into 9 braids and washed at home 0.5.10.20
A post-treatment antibacterial test was performed. As shown in Table 2, 20
Good even after multiple washes [Washing conditions] Neutral detergent used in a commercially available small electric washing machine 1 g/1 Bath ratio 1:100 temperature x time
40℃×5 minutes

Claims (2)

[Claims] (1) In acrylic synthetic fibers, the surface of the metal oxide coated with antibacterial properties is 0.1 to 10%.
An antibacterial acrylic synthetic fiber characterized by containing % by weight. (2) When manufacturing acrylic synthetic fibers by wet spinning, a metal oxide with an average particle size of 0.1 to 5μ, whose surface is coated with an antibacterial metal, is uniformly dispersed in an organic solvent, and then an acrylonitrile-based A method for producing antibacterial acrylic synthetic fibers, which comprises adding and mixing a copolymer to an organic solvent solution and then performing wet spinning.