JPS59179877A - Production of anti-bacterial polymer fiber having vinyl or vinylidene group - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Technical Field The present invention relates to a single-unit fiber (hereinafter referred to as
It is abbreviated as "vinyl chloride or vinylitin group-containing fiber." ), particularly relates to a method for producing hygienic vinyl chloride or vinylitin group-containing fibers having durable antibacterial and antifungal properties.

(b) Conventional technology Fibers containing salt 1-hibinyl or vinylitin groups are fishing nets.

It is used in various fields such as wall cloth, curtains, artificial turf, shoe insoles, etc.

Various molds, germs, and bacteria exist in our living spaces, and their reproduction becomes particularly active in hot and humid environments, causing deterioration and discoloration of fibers.

This caused phenomena such as deterioration, rot, fermentation, and unpleasant odors. Therefore, it has been desired to develop a vinyl chloride or vinylitin group-containing textile product that is cleaner, comfortable, and safe without causing harmful JA.

Conventionally, the antibacterial and anti-mildew processing method has been to apply organic tin and organic mercury compounds to fibers, but recently the toxicity of these compounds has become a problem.

Most of them are now out of use. Recently, CmJ class ammonium salts have been attracting attention as particularly safe antibacterial and fungicidal agents, and silicone quaternary ammonium salts, which are particularly reactive to cellulose fibers, are used as washing-resistant finishing agents. Toshi℃ is attracting attention.

However, in the case of silicone-based quaternary ammonium salts, they exhibit a reactive and durable antibacterial and antifungal effect only on cellulose fibers, but vinyl chloride still exhibits temporary antibacterial and antifungal effects on vinylitin group-containing fibers. Only anti-bacterial and anti-mildew effects can be obtained.It's true, other highly safe anti-bacterial and anti-mildew finishing agents have a certain degree of durability against products containing polyurethane fibers. Although it is said that vinyl chloride (FC) has a bactericidal effect, no processing method has yet been developed that has a durable antibacterial and antifungal effect on vinylitin group-containing fibers.

ri OBJECTS OF THE INVENTION Accordingly, an object of the present invention is to provide a vinyl chloride- or vinylidene-based leprosy-containing fiber that has an excellent antibacterial and antifungal ability.

B) Structure of the Invention The method for producing vinyl chloride- or vinylidene group-containing fibers having antibacterial properties according to the present invention is characterized in that a halogen-containing metal material is applied as an antibacterial finishing agent to vinyl chloride- or vinylidene group-containing fibers. do.

(Preferred Embodiment of the Invention) The vinyl chloride or vinylidene group-containing fiber used in the present invention is made from a polymer having as a main component a group derived from vinyl chloride or a group derived from vinylidene chloride in its two main chains. Any fiber that falls under this definition can be used as a target to be treated in the method of the present invention, but one typical fiber is
Examples include vinyl chloride-vinyl acetate copolymer fibers and vinyl chloride-salt-1-vinyritene copolymer fibers. Fibers containing these salts (vinyl or vinylitine groups) include #Jlta, yarn, woven fabrics, and knitted fabrics consisting of these alone. Alternatively, synthetic fibers such as acrylic, polyester, and polyurethane can be used.

It can also be used in a mixed form by twisting, knitting, interweaving, blending, etc. with regenerated cellulose fibers such as rayon, rayon, acetate, etc., or natural fibers such as cotton.

Antibacterial finishing agent used in the present invention or halogen-containing 1
It has an antimicrobial effect against bacteria and mold, which are microorganisms that live in the natural world, and prevents the growth of bacteria and mold, prevents bad odors caused by spoilage and fermentation, and also reduces the brittleness of clothing. A treatment agent that suppresses hair color and infectious diseases and is safe for the human body is used.Specific examples of such antibacterial agents are:

5-chloro-2-(2,4-dichlorophenoxy)phenol, IL-(fluorodichloromethylthio)-phthalimide, N-dimethyl-N'-7enyl(N'-fluorodichloromethylthio)-sulfami F-1,6 −
Di(4-chlorophenyldiguasito)hexane, short methyl-p-)lylsulfone, N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide, α-bromocinnamaldehyde, and the like are most commonly used.

In the present invention, the antibacterial finishing agent is an organic solvent solution.

It can be applied in the form of an emulsion or an aqueous dispersion, but
In particular, it is advantageous to use it in a form that does not contain an organic solvent and is dispersed in water with a surfactant.

The amount of the antibacterial finishing agent used for the vinyl chloride-based fibers containing vinylidene groups should be adjusted as appropriate depending on the antibacterial activity of the antibacterial finishing agent, the product application in which the vinyl chloride or vinylidene group-containing fibers are used, and the mixing ratio of the fibers. is good, but generally 0 for vinyl chloride or vinylidene group-containing fibers.
0] to 10% owf.

Methods for applying the antibacterial finishing agent to vinyl chloride or vinylidene group-containing fibers include methods such as dipping, dipping, and spraying. After applying by these methods, it is sufficient to dry it.

As a way to further increase the durability of the uninvented antibacterial performance, you can add pre-fix to the antibacterial Roe agent, or
There is a method of applying the entire fixing agent after applying the antibacterial finishing agent.

Anionic phenol fEs hardware is particularly suitable as the fixing agent used in the present invention, and examples of such anionic phenol compounds include tannin, tannic acid, tannic acid/tartarite, phenol sulfonic acid formaldehyde resin, and Novocook. Sulfonated products of type resins, methanesulfonic acid of novolak type resins, methanesulfonic acid of resol type resins, hensyl-hyphenolsulfonic acid, thiophenol compounds, di-hydroxy-di-phenylsulfone compounds, ligand compounds, and Examples include metal chelate f-metallic metals such as cholera.

The fixing agent used is 1 to 20% owf, preferably 3 to 10% owf, based on vinyl chloride or vinylidene group-containing fibers.
%owf range. If the fixing agent is less than 1% owf, the antibacterial durability is about N compared to when it is not used, and if it is more than 20% owf, the antibacterial durability is good, but the texture becomes hard and undesirable. .

The treatment solution used for soaking, padding, or spraying according to the method of the invention may include resin coating agents, softeners,
Antistatic agents, water repellents, etc. can all be added.

(f) Example Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 A screen fabric of Saran (vinylidene chloride fiber manufactured by Asahi Kasei Kogyo ■) was immersed in the antibacterial processing agent solution shown below and in Table 1, and after squeezing the solution (processing agent squeezing rate approximately 30%), it was heated at 120°C. ×6
Dries in 0 seconds. Table 1 shows the anti-mildew performance of the 2t knitted fabric thus obtained.

Screening agent (IIN-(fluorodichlorophenoxy)phenol- (2) N-dimethyl-N'-phenyl (N'-fluorodichloromethylthio) sulfuramide.

(311,6-cy(4-chlorophenylcyquaziniF)
Hexane, (4) Short l Roux P-)! J Lusulfone.

(51N-) liqueur methylthio 4-cyclohexene-1,2-dicarboximide.

(6) α-bromocinnamaldehyde.

(3) 2-(4-thiazolyl)benzimidazole, (Bl 2-methoxycarbonylamino benzimidazole, (C1 zinc-2-bilisimol-1-oxaiF, ([)l p-hydroxymethylbenzoate).

After moistening 1 part of each antibacterial finishing agent with the same amount of acetone, 2 to 3
After adding part of polyoxyethylene nonylphenyl ether and kneading well, and volatilizing the acetone, water was added to prepare a 5% aqueous dispersion (or emulsion) of each antibacterial 710 agent as a processing liquid.

Evaluation method Washing method Knee beads (Kao Soap Co., Ltd.) 2 using a household washing machine
g/It, temperature 40℃, bath ratio 1:40 for 5 minutes (-
1 After that, after dehydrating and dehydrating, 10 while overflowing.
Rinse with water for a minute. This is a total of one wash.

Anti-mildew performance The test was conducted according to JIS-Z-2911.

The test method was to dissolve Czapek Dox agar medium in 50 y/E of water, sieve it to pH=5.5, and sterilize it.

Place in a 90m+nφ sterile petri dish and solidify. Center each test sample on top of this medium.

Aspergillus niger (AT
CC6275) was sprayed on the atomizer at 30°C, and then placed in a constant temperature and humidity tank for 3 days at 30°C and 90% humidity, and the state of image formation was observed.

◎ There is no mold growth on the sample, and an inhibition zone is formed around the sample.

○ No mold growth is observed on the sample.

× The growth of 'd' is observed in ±VC1 of the sample (the size of the sample area).

XX　Top surface of sample 1] Symptoms are observed on the entire surface.

Table 1 As is clear from Table 1, the polyvinylidene chloride fiber fabric produced by the uninvented method has good durability and mildewproof performance.
Ta. However, with methods other than the present invention, the initial anti-mildew performance is good, but the anti-mildew performance disappears after one wash, similar to that of unprocessed products.

Example 2 Sheets, screens and honeycombs made of Zaran fibers 3
Uses a layered insole.

An aqueous dispersion of 5-chloro-2(2,4-dichlorophenogyshi)phenol 2% OWF was used as an antibacterial finishing agent. It was treated with stirring at a bath ratio of 1:40 and a temperature of 60°C for 20 minutes to remove the After the solution, it was dried at 100°C for 2 minutes. Table 2 shows the test results for anti-odor properties, anti-mosquito properties, and wear tests.

Antibacterial performance Heart-in-two John agar medium 'e40.9/J was dissolved in water, sterilized at 120°C, and poured into a 90 mmφ sterile petri dish. On top of this medium, a yellow bulblet (Staphylococcus 7 ureus ATCC) was added.
-6538P) All 4f[i[,, place the sample on it 3
Culture was carried out for 24 hours in a vortex layer at 7°C.'141 determination was carried out in the same manner as fat compaction.

Wear test A test was carried out by 20 people wearing the insole on one arm at 8 o'clock a day, with an unprocessed insole on one shaft and a processed insole on the other. The evaluation of the test results was expressed as the percentage of people who answered that the product had a significant deodorizing effect compared to the unprocessed product.

As is clear from Table 2 below, the shoe insoles processed according to the present invention have excellent durability in terms of anti-fungal and anti-bacterial properties, as well as extremely durable anti-odor properties. It can be seen that the insole is comfortable and hygienic.

Example 3 A knitted fabric made of salt (hibinyl filament (Teviron: manufactured by Teijin)) was used as an antibacterial Roe agent (1) N-dimethyl-
N-phenyl (N'-fluorodichloromethylthio) sulfami F, (2) 5-chloro-2 (2゜4-dichlorophenoxy) phenol was immersed in a 7 wt % aqueous dispersion, and after squeezing (processing agent squeezing) It was dried at 100° C. for 2 minutes (liquid ratio: about 40%). Furthermore, as a comparative example, a dispersion of 2-penzimidazolylyl-rubamic acid methyl ester in 7·\ gravimetric water was treated in the same manner as in the example [7]. Their antifungal performance is shown in Table 3.

As is clear from Table 3 in the margin below, the polysalt (B) vinyl fiber knitted fabric produced by the method of the present invention had superior mold-proofing performance with excellent washing durability. The initial anti-mildew properties of the anti-fungal agent were good, but after one wash, a product with no anti-mildew properties similar to the unprocessed product was obtained.

patent applicant Asahi Kasei Industries, Ltd. patent application agent Patent attorney Akira Aoki 5P Principle” = Nishi Tate Kazuyuki Patent attorney Yukio Uchida Patent attorney Akira Yamaguchi

Claims (1)

[Scope of Claims] 1. A vinyl chloride group or vinylidene chloride containing antibacterial property characterized in that a halogen-containing compound is added as an antibacterial finishing agent to a polymer fiber containing a vinyl chloride group or vinylidene chloride group as a main component. A method for producing a polymer fiber containing a group as a main component. 2. The antibacterial finishing agent is 5-chloro-2-(2,4-dichlorophenoxy)phenol, N-(7A-fluorodichloromethylthio)-phthalimide, N-dimethyl-N'-7enyl(N'-fluorodichloromethylthio) )-sulfamide, 1,6-di(4-chlorophenylcyquadinito)hexane-shortmethyl-P-tolylsulfone+
N-)dichloromethylthio-4-cyclohexene-1
, 2-dicarboximide, and α-bromocinnamaldehyde, which contains as a main component an antibacterial vinyl chloride group or a vinylidene chloride group as claimed in claim 1. Method of manufacturing polymer fibers.