JP2000119960A - Antibacterial and antifungal processing of fibers - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method for imparting antibacterial and antifungal properties to synthetic fibers and semi-synthetic fiber products against methicillin-resistant Staphylococcus aureus and many other fungi and molds. SOLUTION: General formula [I] (Wherein, M represents a divalent metal atom).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to synthetic fibers such as polyester fibers, acrylic fibers and nylon fibers, semi-synthetic fibers such as acetate fibers, and mixed fibers of these fibers and natural fibers. To impart antibacterial and antifungal properties to textile products. In particular, the present invention relates to a processing method for imparting antibacterial properties to Staphylococcus aureus, methicillin-resistant Staphylococcus aureus (MRSA) Klebsiella pneumoniae, Escherichia coli, pathogenic Escherichia coli O157, and Pseudomonas aeruginosa. Further, the present invention relates to a processing method capable of imparting antibacterial and antifungal properties having extremely high washing resistance.

[0002]

2. Description of the Related Art With the increasing hygiene orientation of textile products such as textiles for clothing, curtains, towels, wall cloths and the like, antibacterial and antifungal processing methods for various textile products are actively developed. In addition, in recent years, the so-called nosocomial infection problem in medical practice has been greatly highlighted, and as a countermeasure, research on antibacterial and antifungal processing technology for textile products in medical facilities such as surgical gowns, sheets and partition curtains is urgently needed. Have been.

[0003] Antibacterial and antifungal processing techniques for products made of synthetic fibers and the like include a synthetic fiber having an antibacterial and antifungal property by kneading an agent such as an antibacterial agent or an antifungal agent into a spinning solution of the synthetic fiber and spinning. A method of producing fibers and mixing and weaving them with other fibers as necessary to obtain a product, or weaving by mixing normally spun fibers and other fibers as necessary There is a method of attaching an antibacterial agent or an antifungal agent to the cloth obtained by sewing, and also to the product obtained by sewing it. Immersed in a solution containing, impregnated with a solution containing an antibacterial agent or an antifungal agent to the method of heating and fibers and textiles,
Then, there is a method of heating, and further, a method of attaching an antibacterial agent or an antifungal agent to fibers and fiber products using a binder resin.

[0004]

However, the products obtained by any of these methods are weakened by new resistant bacteria that appear one after another, and are washed more effectively. Therefore, it is required that a new chemical agent imparts antibacterial and antifungal properties with stronger washing resistance. The emergence of more resistant bacteria such as methicillin-resistant staphylococci, so-called MRSA and more recently vancomycin-resistant enterococci (VRE),
On the other hand, the development of a new antibacterial and antifungal processing technology that can withstand harsh industrial laundering such as specified by the Textile Products New Function Evaluation Council (abbreviated as SEK) and hospital linen supply is awaited. ing. The inventor has
Earlier, extensive research was conducted on methods for imparting antibacterial and fungicidal properties to polyester fiber products, and an extremely effective method was developed (see Japanese Patent Publication No. 5-12475).
However, he continued his research, and found a very effective method in the research to further develop based on this result.

The present invention can impart strong antibacterial properties to fibers mainly composed of synthetic fibers against MRSA, Staphylococcus aureus, Escherichia coli, pathogenic Escherichia coli O157: H7 and Pseudomonas aeruginosa. It is intended to provide a new processing method.

[0006]

According to the present invention, fibers are represented by the general formula [I]:

[0007]

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[0008] The subject matter of the present invention is an antibacterial and antifungal treatment method for fibers, which is treated with a compound represented by the formula (wherein M represents a divalent metal atom). Less than,
The present invention will be described in detail.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The fibers to which the present invention is applied include synthetic fibers such as polyester fibers, nylon fibers and polyacrylonitrile fibers, semi-synthetic fibers such as acetate fibers, and mixed fibers of these fibers and natural fibers. Is mentioned. Examples of the form of the fiber include yarn, woven fabric, and various products.Examples of the product include clothing, bedding, bedding, rugs, curtains, indoor wall cloth, and the like, especially surgical gowns used in medical facilities such as hospitals, Products include bedclothes such as nursing clothes and sheets, partition curtains, bandages, towels, towels, and the like.

The antibacterial and antifungal agents used in the present invention include:
The compound represented by the general formula [I] is exemplified, and among them, a substance in which M is Zn, and a pyrithione zinc complex are most preferable. This is because Zn is an essential component of the human body and has features such as high safety, and the compound containing Zn is hardly absorbed transdermally.

Because of these properties, the compounds have a track record of being widely used in the fields of cosmetics and shampoos. When treating fibers with a pyrithione complex such as zinc pyrithione, it is generally applied in the form of an aqueous emulsion or suspension of the compound.
Preparation of the treatment solution, each component may be weighed and prepared each time, but in advance, a high concentration stock solution is prepared, weighed and diluted according to the amount of fibers to be treated, and diluted. Convenient to use.

The high concentration stock solution may be in the form of a solution (emulsion) or an aqueous suspension. In order to prepare a solution in the form of a solution, for example, a polar solvent such as dimethyl sulfoxide (DMSO), a surfactant such as styrenated phenol, and other emulsion stabilizers are blended to make a uniform liquid. To prepare an aqueous suspension-type stock solution, anionic dispersants such as polynaphthalenesulfonate and ligninsulfonate; nonionic dispersants such as styrenated phenol and polyoxyethylene hydrogenated castor oil; Ammonium salt-based cationic dispersant or a dispersant consisting of a mixture thereof and water, if necessary, a thickener, an antifreezing agent and an antifoaming agent are added to form a slurry, and a ball mill, a ceramic mill or a pearl mill is used. It is pulverized to an average particle size of 6 μm or less, preferably 3 μm or less to obtain an aqueous suspension having a concentration of 4-80% by weight of the pyrithione complex.

The antibacterial and antifungal processing methods for fibers according to the present invention are roughly classified into a dipping method and a padding method. First,
The immersion method uses a pyrithione complex of 0.001 to 20.0% based on the weight of the fiber to be processed in a pressure-resistant closed container when processing under pressure and in an open container when performing under normal pressure. The bath ratio is 1: 5 to 50, the treatment temperature is 70 to 160 ° C., and the treatment time is 5 to 90 minutes.

The polyester fiber is pressurized under a pressure of 120 to 14
At 0 ° C, under normal pressure for nylon and acetate fibers,
It is desirable to process at 80 to 100 ° C. The padding method is a method of impregnating a processing solution using a padding device and then fixing the mixture by heating. In the case of a fiber in which a pyrithione complex is not easily fixed, such as a polyester fiber, the heating temperature is set to 110 to 230 ° C. , High temperature steam heating treatment (so-called pad steam method), other molten metal method, molten salt method,
It is performed by a thermosol method.

[0015] The content of the pyrithione complex in the treatment liquid is 0.1.
01-50 g / l, squeezing rate 40-90% (weight),
The heat treatment temperature is 80 to 230 ° C, and the treatment time is 10 seconds to 10
The selection is appropriately performed from the range of minutes. Also in the padding method, when processing polyester fibers, as described above, high temperature, preferably 130 to 230 ° C.
However, nylon fibers and acetate fibers need to be fixed at a relatively low temperature, specifically 70 to 1
Can be fixed at 10 ° C.

The processing method of the present invention can be applied simultaneously with dyeing and further with other fiber processing such as flameproofing. In particular, since the processing conditions in the present invention hardly differ from the processing conditions for dyeing, they can be incorporated into the dyeing process. In addition, the waste liquid discharged when the present invention is carried out, since the pyrithione complex as a chemical may reduce the activity of the activated sludge used in the wastewater treatment, the waste liquid is treated with sodium hypochlorite or excess water. Decomposition using an oxidizing agent represented by hydrogen oxide, a reducing agent such as hydrosulfite, or a combination of the reducing agent and slaked lime is also performed as necessary.

Further, the waste liquid is used as a polychelating agent represented by a divalent or trivalent iron compound and a hydrocarbon compound having a dithiocarbamic acid group and a thiol group, for example, Miyoshi Oil & Fat Co., Ltd.
If necessary, a method of treating with Epofloc L-1 (trade name) and / or a polymer flocculant such as sodium polyacrylate or acrylamide to coagulate sedimentation and separation of the pyrithione complex in the waste liquid is also carried out. Is done.

[0018]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the washing method and various test methods in an Example were implemented according to the following method.

<Test Method> Washing method 1) JIS L0217-103 (home washing at 40 ° C). JIS L1042-F2 (60 ° C industrial washing) 2) SEK. Washing method by specific bacteriostatic processing (using a standard combination detergent of JAFET, washing is repeated 50 times under a predetermined condition of 80 ° C. In this example, 100 washes were also performed. ) Antibacterial test Two species of Staphylococcus
aureus FDA209P and methicillin-resistant Staphylococcus aureus: MRSA), Klebsiel
la pneumocniae IFO13277),
Escherichia coli IF ( Escherichia coli IF)
O3301 and E. coli O157: H7) and Pseudomonas aeruginosa.
IFO3755), the viable cell count of unprocessed cloth and processed cloth was measured by the unified test method of SEK. Judgment of the antibacterial evaluation was evaluated as valid (O) when the number of recovered bacteria of each test cloth was less than the number of inoculated bacteria, and invalid (X) when the number was more than that.

In the table, S is Staphylococcus aureus, M is Methicillin-resistant Staphylococcus aureus, E is E. coli, E is pathogenic E. coli O157: H7, EO is K, K. pneumoniae is P, and P.
Respectively. 2) Antifungal test In accordance with JIS Z 2911, a fiber product was evaluated according to the following judgment in accordance with the mold resistance test method.

[0021]

[Table 1]

In each example, the stock solutions described below were diluted and used. Emulsion-type stock solution The following components were stirred using a mixer to form a uniform emulsion. Zinc pyrithione or Copper pyrithione 4 parts by weight Polyoxyethylene styrylphenyl ether (emulsifier) 10 parts by weight Dimethyl sulfoxide (solvent) 86 parts by weight

Aqueous suspension-type stock solution The following components were mixed and made into a paste, and then an aqueous suspension having an average particle size of 0.6 μm was obtained using a ceramic mill. Zinc pyrithione or Copper pyrithione 20 parts by weight Polyoxyethylene hydrogenated castor oil (dispersant) 3 parts by weight Sodium polyacrylate (thickener) 0.5 parts by weight Glycerin (antifreeze) 2 parts by weight Purified water 74.5 parts by weight Department

Further, the following three kinds were selected as comparative control drugs, and a 20% by weight aqueous suspension stock solution thereof was prepared in the same manner as described above. Comparative control drug para-chlorometaxylenol (abbreviated as PCMX in the table) N- (fluorodichloromethylthiophthalimide (abbreviated as FFP in the table) α- [2-4 (chlorophenyl) ethyl] -α- (1,
1-dimethylethyl) -1H-1,2,4-triazoleethanol (in the table,
(Abbreviated as TSK)

Example 1 Polyester woven fabric (abbreviated as T in the table), polyester / cotton 85/15 mixed woven fabric (abbreviated as T / C in the table),
Table 1 for each of triacetate woven fabric (abbreviated as A in the table) and nylon woven fabric (abbreviated as NY in the table)
Under the processing conditions shown in the above, the processing is performed at a bath ratio of 1:10,
Thereafter, the substrate was washed with water, reduced, and washed with water, and dried at 130 ° C for 2 minutes. In addition, polyester woven fabric and polyester / cotton 8
The 5/15 mixed woven fabric was heat-set at 190 ° C. for 30 seconds and then subjected to 100 industrial washes. One household wash on triacetate and nylon woven fabrics
It was performed 00 times. An antibacterial test was performed on each of the obtained woven fabrics, and the evaluation results shown in Table 2 were obtained. As is clear from the description in Table 2, each woven fabric processed according to the method of the present invention exhibits sufficient antibacterial properties even after washing under severe conditions.

[0026]

[Table 2]

Example 2 Sumikaron Red E-FBL as dye
0.02% owf Sumikaron Blue E
Using FBL 0.002% owf (disperse dye manufactured by Sumitomo Chemical Co., Ltd.), zinc pyrithione 2% owf is present as an antibacterial and antifungal agent, and a polyester woven fabric is subjected to bath ratio using a liquid high-pressure dyeing machine. 1:15, pH 5.5, 130 ° C,
Staining and antibacterial and antifungal processing were performed under the conditions of 60 minutes. Next, post-treatment and washing were performed in the same manner as in Example 1. The obtained processed cloth showed sufficient antibacterial properties and mold resistance 3 even after predetermined washing. On the other hand, when the same processing was performed using PCMX as a comparative control agent instead of zinc pyrithione, no antibacterial and antifungal activity was exhibited.

Example 3 Polyester woven fabric and polyester / cotton (90/10)
The mixed woven fabric was impregnated with the treatment solution having the concentration shown in Table 2, and the squeezing rate was 8%.
Squeezing so as to be 0%, and performing immobilization treatment by each method of thermosol method, superheated steam method or high pressure steam method,
Next, post-treatment and washing were performed in the same manner as in Example 1.
The obtained woven fabric was tested for antibacterial properties and mold resistance, and the results are shown in Table 3.

As is evident from the description in Table 3, the polyester woven fabric fixed by heating at a high temperature of 130 ° C. or more using zinc pyrithione maintained sufficient antibacterial and antifungal properties even after severe washing. When the same processing was performed using PCMX as a comparative control agent instead of zinc pyrithione, no antibacterial and antifungal activity was observed.

[0030]

[Table 3]

Example 4 Nylon woven fabric, acrylic woven fabric (abbreviated as AC in the table)
And diacetate woven fabric (abbreviated as DA in the table) in Table 3
Antibacterial treatment was performed using the described chemicals at a bath ratio of 1:10 under the processing conditions shown in Table 4. Next, antibacterial evaluation was performed 50 times after home washing, and the results are shown in Table 3.

[0032]

[Table 4]

Example 5 The following method was carried out as a method for treating a waste liquid containing a pyrithione metal complex. The wastewater discharged in the examples containing 220 ppm of zinc pyrithione (160 ppm as pyrithione) was treated under the treatment conditions shown in Table 5, the residual amount of zinc pyrithione was quantified, and the results are also shown in the same table. did. The effect was sufficiently confirmed by any of the methods.

[0034]

[Table 5]

[0035]

According to the present invention, MRSA, bacteria such as Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa and the like can be used for artificial fiber products such as polyester, acrylic, nylon and acetate and mixed fiber products of these and natural fibers. The fungus can be treated to exhibit antibacterial and antifungal properties, and the antibacterial and antifungal properties imparted can withstand severe washing. It has a great effect on prevention. Furthermore, the safety of the processed fibers is high, and a method for treating waste liquid generated by the processing has been established, and there is no concern about adverse effects on the environment.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yasuo Kosako 2-6-11 Nakajima, Yodogawa-ku, Osaka-shi, Osaka Inside Osaka Chemical Co., Ltd. No. 11 Osaka Chemical Co., Ltd. F term (reference) 4H011 AA02 AA03 BA01 BB09 BB16 BB18 BC19 DA15 DC10 DD07 DE03 DE10 4L033 AA04 AB01 AC10 AC15 BA44

Claims (4)

[Claims] 1. The fiber is represented by the following general formula [I]: (Wherein M represents a divalent metal atom). A method for antibacterial and antifungal processing of fibers, comprising treating with a compound represented by the formula: 2. The fibers are mainly composed of synthetic fibers, and the treatment is carried out by immersing the fibers in an aqueous dispersion of the compound represented by the general formula [I], and applying a pressure of 110 to 160 ° C.
The antibacterial and antifungal processing method for fibers according to claim 1, comprising a method of heat-treating the fibers or impregnating the fibers with an aqueous dispersion of the compound, and then heat-treating the fibers at 110 to 230 ° C. 3. The method according to claim 1, wherein M in the general formula [I] is Zn. 4. The antibacterial and antifungal processing method according to claim 1, wherein an oxidizing agent or a reducing agent is added to the discharged waste liquid to convert the compound represented by the general formula [I]. An antibacterial and antifungal processing method for fibers which decomposes or coagulates and separates the compound using a polychelating agent or a polymer flocculant.