JP2849017B2 - Manufacturing method of antibacterial fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for preventing coloring of antibacterial fibers containing a silver-based inorganic antibacterial agent.

[0002]

2. Description of the Related Art It has long been known that silver ions have antibacterial properties. For example, it is widely used as a disinfectant or bactericide in the form of an aqueous solution of silver nitrate. Various methods have been proposed as methods for applying the antibacterial properties of silver ions to fibers. For example, an antibacterial agent in which silver ions are supported on zeolite solid particles, an antibacterial agent in which silver ions are supported in a phosphate or condensed phosphate, and an antibacterial agent in which silver ions are supported in a calcined product of hydroapatite This is a method of imparting antibacterial properties by kneading an inorganic antibacterial agent such as the above into fibers.

[0003] However, when these antibacterial agents are used, there has been a problem that coloring and discoloration which are considered to be caused by the action of silver ions occur frequently.

[0004] For example, there is an unexpected problem that an oil component, an antistatic agent, a softening agent and the like applied to the fiber are colored by the action of silver ions, and the product before shipment becomes dirty and cannot be shipped. This is because some of the oil component and antistatic agent components reacted with silver ions or oxidized silver ions,
It is considered that the product was colored blackish brown.

On the other hand, it has been proposed to add various stabilizers to a resin containing an antimicrobial agent to coexist with the antimicrobial agent in order to prevent unexpected discoloration such as photodeterioration due to ultraviolet rays or the like. . For example, benzotriazole-based compounds, oxalic acid anilide-based compounds, salicylic acid-based compounds, hindered amine-based compounds are used as anti-deterioration (coloring) agents to be added to an antibacterial resin composition comprising a resin and an antibacterial zeolite carrying silver ions. And hindered phenol compounds are known (JP-A-63-2
No. 65958).

However, this prior document does not disclose any attempt to prevent the above-mentioned coloring and discoloration caused by silver ions, but does not disclose any such solution.

[0007]

SUMMARY OF THE INVENTION Accordingly, the present inventors
The present inventors have conducted intensive studies with the aim of providing a method for preventing oxidation and coloring of silver ions by oils and the like while maintaining the antibacterial properties of silver ions.

[0008]

That is, the present invention relates to an antibacterial fiber containing a silver-based inorganic antibacterial agent, and the following general formula (I):

[0009]

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(Wherein R ¹ is hydrogen or a lower alkyl group, and R ² is hydrogen or an alkali metal). An azole compound having no mercapto group is contained as a coloring inhibitor, except for the compound represented by the formula: A method for producing an antibacterial fiber, comprising contacting a treatment liquid.

Hereinafter, the present invention will be described in detail.

The silver-based inorganic antibacterial agent used in the present invention is not particularly limited as long as it is an inorganic compound carrying silver ions.
Examples thereof include inorganic adsorbents such as silica gel, and inorganic ion exchangers such as zeolite, hydroxyapatite, zirconium phosphate, titanium phosphate, potassium titanate, hydrous antimony, hydrous bismuth, hydrous zirconium oxide, and hydrotalcite.

The method of supporting silver ions on these inorganic compounds is not particularly limited, but specific examples include a method of supporting them by physical adsorption or chemical adsorption, a method of supporting them by ion exchange reaction, and a method of supporting them by a binder. A method in which a silver compound is loaded by driving an inorganic compound into an inorganic compound, a method in which a thin layer of a silver compound is formed on the surface of the inorganic compound by a thin film forming method such as vapor deposition, dissolution deposition reaction, or sputtering. is there. Among the above inorganic compounds, an inorganic ion exchanger is preferable because it can strongly support silver ions. Among silver-based inorganic antibacterial agents, preferred are JP-A-3-83905 and JP-A-3-83905.
And zirconium phosphate described in JP-A-83906.

The amount of the inorganic antibacterial agent added to the fibers is as follows:
Although it depends on the type of the agent, it is about 0.1 to 10%, preferably 0.5 to 3.0%. The polymer constituting the antibacterial fiber containing these inorganic antibacterial agents is not particularly limited, and specifically, polyamides such as nylon 6, nylon 66, polyethylene terephthalate, polyesters such as polybutylene terephthalate, polyethylene, polypropylene And synthetic resins such as polyolefins, polyvinyl alcohols, acrylic resins, and polyurethanes.

The method of compounding these inorganic antibacterial agents into the fiber may be either at the time of polymerizing the fiber material or at the time of melt-spinning or adding it during dissolution in a solvent and uniformly kneading and dispersing. Good. Preferably, a method of kneading an inorganic antibacterial agent into fibers is used.

The coloring inhibitor used in the present invention has the following general formula (I):

[0017]

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(Here, R ¹ is hydrogen or a lower alkyl group, and R ² is hydrogen or an alkali metal.) Except for compounds represented by the following formula, azole compounds having no mercapto group (hereinafter referred to as azole compounds) It is.

Specific examples of the azole compound include azoles such as imidazole, oxazole, thiazole, selenazole, triazole and tetrazole. A benzothiazole having a benzene ring;
The azole ring may be combined with other atomic groups, such as benzimidazole. Preferably, benzothiazole and benzimidazole are mentioned, and when they are used by being contained in an aqueous treatment solution, their potassium salts are mentioned.

These coloring inhibitors are contained in the processing solution,
Contacted with antibacterial fibers. Here, the treatment liquid is not particularly limited as long as it is a treatment liquid used between spinning and higher processing steps. Specifically, a spinning oil (emulsion or straight), an after oil, a coning oil (mineral oil or Ester-based leveling agent), a dyeing solution containing a leveling agent or a slow dyeing agent, or a solution containing a softening agent, an antistatic agent, a finishing oil agent, a waterproofing agent, and the like.

After the final product is obtained, it may be mixed with a liquid containing a softening agent, a bleaching agent, a mold removing agent and the like, and applied to the surface.

The preferred compounding ratio of the colorant is 0.0 to 100 parts by weight (hereinafter simply referred to as "parts") of the processing solution.
05 to 5 parts, more preferably 0.05 to 0.5 part. If the amount is less than 0.005 part, the coloring of the antibacterial fiber may not be sufficiently suppressed. On the other hand, if the amount is more than 5 parts, the effect of preventing coloring is hardly improved, but rather, in each step. There is a possibility that the processing solution may have an adverse effect on the effects to be originally exhibited.

The treatment liquid in the present invention is prepared by adding the above-mentioned coloring inhibitor and azole compound to the treatment liquid at an appropriate temperature and pressure according to the characteristics of the fiber to be treated, while heating and pressurizing or depressurizing as necessary. They can be easily prepared by mixing, mixing or kneading them, and their specific operations may be performed by a conventional method.

Since there are hydrophilic and lipophilic compounds depending on the type of the azole compound, a sufficient effect can be obtained by appropriately selecting and using the type of the azole compound having high solubility or dispersibility depending on the characteristics of the processing solution. Can be.

In order to prepare the processing solution of the present invention, the coloring inhibitor of the present invention may be added to a composition conventionally used as various processing solutions at an appropriate concentration. An example is shown below. However, the composition is in parts by weight.

Spinning oil lubricant leveling agent: trimethylolpropane tridecanoate 47 emulsifier: POE (n) hydrogenated castor oil trilaurate 25 POE (25) trimethylolpropane trilaurate 5 POE (n) nonylphenol ether 15 isocetyl phosphate K salt 5 benzol Thiazole K salt 3 After oil agent : PEG (200) dioctanate 85 POE (25) hydrogenated castor oil triolate 10 Benzothiazole 5 Dyeing solution : Commercially available Siglegal (registered trademark) 95 Benzimidazole K salt 5 Softener: Commercially available humming ( (Registered trademark) 95 Benzothiazole K salt 5

[0027]

The mechanism of preventing the coloration of these azole compounds is not clear, but it is presumed that the amide group (NH) in the azole compound forms a chelate compound with a small amount of dissolved silver ion to form a chelate compound, and the activity of the silver ion is reduced. It is presumed that killing prevents the oil agent from being oxidized and deteriorated, and conversely prevents silver ions from being oxidized to form silver oxide (AgO), thereby preventing coloring.

[0028]

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When the azole compound is contained in the treating solution and brought into contact with the antibacterial fiber, the azole compound adheres to the fiber surface, so that the coloring can be efficiently prevented. On the other hand, when the azole compound is kneaded into the fiber and used, the proportion of the coloring inhibitor on the fiber surface becomes extremely small, so that the coloring preventing effect cannot be exerted. Further, since the melting temperature of the coloring prevention agent is low, it hardly volatilizes at a normal spinning temperature, so that the effect cannot be exhibited.

[0030]

According to the method of the present invention, it is possible to obtain an antibacterial fiber in which coloring is prevented while maintaining antibacterial properties.

[0031]

The present invention will be described in more detail with reference to the following examples. In addition, each measuring method in an Example was calculated | required by the following method.

(Evaluation of antibacterial properties) Fibers to which an antibacterial agent was added were prepared, and the antibacterial properties of the fibers were evaluated using a shake flask method. A suspension of test bacteria (Escherichia coli or Staphylococcus aureus) is poured into the sample, and the suspension is sealed 150 times /
After shaking for 1 minute, the number of viable bacteria after the shaking was counted, and the difference in the reduction rate (%) with respect to the initial number of bacteria in the poured suspension was further evaluated for antibacterial activity. (Based on SEK Standards of the Textile Sanitary Processing Council)

(Evaluation of coloring property) Fibers to which an antibacterial agent was added were prepared, and POE (25) hydrogenated castor oil triolate (stock solution) was adhered thereto as a model substance of soil.
The state of coloring after standing for 24 hours was evaluated based on whether the stain was large or small.

[0034]

EXAMPLE 1 and Comparative Example 1 Nylon 6 melt spinning, this time, with respect to the molten polymer, zirconium phosphate compound was supported silver ions _{[Ag x H y Na z Zr} 2 (PO
₄ ) ₃ ] (x + y + z = 1, x = 0.3, y = 0.5,
z = 0.2) was added and dispersed so that the concentration in the yarn became 1%, and an antibacterial nylon crimped fiber (1300 denier / 68 filament) was prepared. In order to impart smoothness to the fiber before winding, 0.5% of after oil (a mixture of trimethylpropane / tridecane and POE (25) hydrogenated castor oil triolate) was applied to the yarn. At this time, 5% of benzothiazole was added to the after oil as an anti-coloring agent. When not added, the wound crimped fiber cheese was colored blackish brown and could not be shipped as a product.

When benzothiazole was added, there was no coloring, and the antibacterial properties of both Escherichia coli and Staphylococcus aureus were evaluated. As a result, good antibacterial properties were obtained with a sterilization rate of 90% or more in each case.

[0036]

Examples 2 to 3 and Comparative Examples 2 to 4 Polyester was melt-spun. At this time, antibacterial zeolite particles carrying silver ions with respect to the molten polymer were adjusted to a concentration of 1.5% in the yarn. It was added and dispersed to produce antibacterial PET fiber (1000 denier / 136 filament). Before winding, a benzimidazole K salt as an anti-coloring agent was made into an emulsion and applied to the fiber. At that time, the relationship between the agent concentration of the emulsion and the optimum amount of adhesion was examined by varying the amount of adhesion. As a stain substance, a stock solution of (A) POE (25) hydrogenated castor oil trilaurate and (B) a softener Humming (registered trademark) is applied to the surface of the rolled cheese and left for a whole day and night. And E. coli were evaluated for antibacterial activity. Table 1 shows the results.

[0037]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ identification code FI C08K 3/10 C08K 3/10 (58) Field surveyed (Int.Cl. ⁶ , DB name) D06M 13/00-13/535 D01F 1/10 D01F 6/90-6/92

Claims (1)

(57) [Claims] An antibacterial fiber containing a silver-based inorganic antibacterial agent, and the following general formula (I): (Wherein, R ¹ is hydrogen or a lower alkyl group, R ²
Is hydrogen or an alkali metal. A method for producing an antibacterial fiber, which comprises contacting a treatment liquid containing an azole compound having no mercapto group as a coloring inhibitor, excluding the compound represented by the formula (1).