JP2555258B2 - Resin molded product having antibacterial and antifungal properties and method for preventing coloring of the resin molded product - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin molded product having antibacterial and antifungal properties, and a method for preventing coloring of the resin molded product.

[0002]

2. Description of the Related Art Generally, 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 property of silver ions to fibers. For example, an antibacterial agent in which zeolite solid particles carry silver ions, an antibacterial agent in which phosphate-based or condensed phosphates carry silver ions, and an antibacterial agent in which calcined hydroapatite carries silver ions. It is a method of imparting antibacterial properties by kneading an inorganic antibacterial agent such as

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

[0004] For example, there is an unexpected problem that oil components, antistatic agents, softening agents, etc. applied to fibers are colored by the action of silver ions, and the products before shipping are soiled and cannot be shipped. This is because some oil components 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 that various stabilizers be added to the resin to coexist with the antibacterial agent for the purpose of preventing an unexpected discoloration of the resin containing the antibacterial agent due to photodegradation due to ultraviolet rays or the like. . For example, as a photodeterioration (coloring) inhibitor to be added to an antibacterial resin composition comprising an antibacterial zeolite carrying silver ions and a resin, a benzotriazole compound, an oxalic acid anilide compound, a salicylic acid compound, a hindered amine compound And hindered phenol compounds are known (Japanese Patent Laid-Open No. 63-2.
65595).

[0006] However, in this prior document, let alone the recognition to prevent the above-mentioned coloring and discoloration due to silver ions, no such solution is disclosed.

As an antifungal agent, 2- (4-thiazole) benzimidazole is commercially available, and the above publication also describes that the antibacterial zeolite itself substituted with antibacterial metal ions has antifungal properties. Has been done.

[0008]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a resin molded product which does not cause oxidation or coloring of silver ions due to an oil agent and a resin molded product having antibacterial and antifungal properties while maintaining antibacterial and antifungal properties. It is to provide a method for preventing coloration of a product.

[0009]

[Means for Solving the Problems] That is, the present invention provides a resin molded product and a resin in which a silver-based inorganic antibacterial agent and a mercapto group-free (benzazole) / azole compound are kneaded in a resin. A method for preventing coloration of a resin molded product having antibacterial and antifungal properties, which comprises kneading a silver-based inorganic antibacterial agent and a mercapto group-free (benzazole) / azole compound therein.

The present invention will be described in detail below. The silver-based inorganic antibacterial agent used in the present invention is not particularly limited as long as it is an inorganic compound supporting silver ions, specifically, activated carbon, activated alumina, an inorganic adsorbent such as silica gel, zeolite, Hydroxyapatite,
Inorganic ion exchangers such as zirconium phosphate, titanium phosphate, potassium titanate, hydrous antimony oxide, hydrous bismuth oxide, hydrous zirconium oxide and hydrotalcite can be mentioned.

The method of supporting silver ions on these inorganic compounds is not particularly limited, and specifically, for example, a method of supporting by physical adsorption or chemical adsorption, a method of supporting by an ion exchange reaction, a method of supporting by a binder. And a method of supporting by injecting a silver compound into an inorganic compound, a method of supporting by forming a thin layer of a silver compound on the surface of the inorganic compound by a thin film forming method such as vapor deposition, dissolution precipitation reaction, and sputtering. is there. Among the above-mentioned inorganic compounds, the inorganic ion exchanger is preferable because it can firmly support silver ions. Among the silver-based inorganic antibacterial agents, preferred are those disclosed in JP-A-3-83905 and JP-A-3-83905.
The zirconium phosphate salt described in JP-A-83906 can be mentioned.

The amount of the silver-based inorganic antibacterial agent added to the molded article depends on the type of the agent, but is about 0.1 to 10% by weight (weight of the molded article), preferably 0.5 to 3%. It is 0.0% by weight.

The resin to which these silver-based inorganic antibacterial agents are added is not particularly limited, but specifically, polyamide resins such as nylon 6 and nylon 66, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyethylene, Examples thereof include olefins such as polypropylene, polyvinyl alcohol, synthetic resins such as acrylic resin and urethane resin, and synthetic fibers.

The silver-based inorganic antibacterial agent may be added to the molded article either during the polymerization of the resin or the fiber raw material, or during the melt spinning or while it is dissolved in the solvent and uniformly kneaded. It may be dispersed.

On the other hand, in the present invention, a (benzazole) azole compound having no mercapto group (hereinafter simply referred to as (benzazole) azole compound) is kneaded into the resin together with the above-mentioned silver-based inorganic antibacterial agent. According to the present invention, a resin molded product which is not colored is obtained. That is, it has been found that the above-mentioned (benzazole) -azole compound, which is conventionally known as an antifungal agent, has a function as a coloring preventing agent by silver. Specific examples of the (benzoazole) / azole compound include a thiazole / benzotriazole compound,
Examples thereof include thiazole / benzimidazole compounds. Particularly, the 2- (4-thiazole) benzimidazole compound is preferable because it is highly safe and mainly supplements the antifungal property of the silver-based inorganic antibacterial agent having a strong action as an antibacterial agent.

Further, the reason why the (benzazole) -azole compound having a mercapto group is excluded is that the mercapto group has a high reactivity with silver ions, but the use of the compound has an effect of preventing coloration. The antibacterial property is also lost, and the original function as a resin molded product having antibacterial and antifungal properties is lost, which is meaningless. It is presumed that this is because the reactivity between the mercapto group and the silver ion is high, and even the silver ion in the silver compound body ion-exchanged with the inorganic ion exchanger reacts with the mercapto group to lose the antibacterial property. .

The method for adding the (benzazole) azole compound to the molded article is usually 0.01
It is preferable to add about 5.0% by weight of powder and uniformly melt blend.

The addition amount of the (benzazole) azole compound may be the minimum amount for capturing silver ions,
It is not preferable to add it extra. It is usually less than or equal to the amount of the silver-based inorganic antibacterial agent added. As an example, 0.01 to 5.0% is added to a fiber to which 1% of an inorganic ion exchanger (silver-substituted zirconium phosphate) having a silver ion substitution rate of 3% is added.
About (weight), preferably about 0.1 to 2.0% of (benzazole) azole compound may be added. When the content of the agent is 0.01% or less, the anti-coloring effect is not exhibited, and when the amount of the agent is equal to or more than the antibacterial agent; Is not exposed, and the antifungal property is good, but the antibacterial property is lowered, which is not preferable.

Further, both the silver-based inorganic antibacterial agent and the (benzazole) azole compound used in the present invention have high heat resistance and can be kneaded in the stage of melt spinning of resin or fiber. is there.

[0020]

Although the mechanism of preventing coloration by these (benzazole) azole compounds is not clear, it is possible that the amide group (NH) in the azole ring forms a chelate compound with the dissolved silver ion. To prevent the oxidative deterioration of the oil agent, and conversely to prevent silver ions from being oxidized to form silver oxide (AgO), thereby preventing coloring. It is estimated to be.

[0021]

Embedded image

[0022]

The resin molded product obtained by the present invention is
It is a resin molded product that maintains its antibacterial and antifungal properties while preventing coloration.

[0023]

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 property) Fibers or resins to which an antibacterial agent was added were prepared and the antibacterial property was evaluated by using the shake flask method. A suspension buffer of test bacteria (Escherichia coli and Staphylococcus aureus) was added to the sample piece and
The mixture was shaken at 50 times / min for 1 hour, the viable cell count after the shaking was measured, and the antibacterial activity was evaluated by the difference (%) in the reduction rate with respect to the initial cell count of the suspension suspension. (Compliant with the SEK standard of the Textile Products Sanitary Processing Council)

(Evaluation of Coloring Property) Fibers or resins to which an antibacterial agent was added were prepared, and POE (25) hydrogenated castor oil trioleate (stock solution) was applied thereto as a model substance for stains, and the coloring state after standing for 24 hours. Was evaluated by the degree of dirt.

[0026]

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 was 1% to prepare an antibacterial nylon crimped fiber (1300 denier / 68 filament). After-oil (a mixture of trimethylpropane tridecanate and POE (25) hydrogenated castor oil trioleate) was applied at 0.5% to the yarn to impart smoothness to the fiber before winding. At this time, 2- (4-thiazole) benzimidazole as a coloring preventing agent was added to the polymer in an amount of 0.5% in the melting stage. When it was not added, the rolled-up crimped fiber cheese was colored dark brown and could not be shipped as a product.

When 2- (4-thiazole) benzimidazole was added, there was no coloring, and the antibacterial properties were evaluated by both Escherichia coli and Staphylococcus aureus.
Good antibacterial properties of 9% or more were obtained. Further, when this yarn was tufted or dyed and carpeted, the product to which the anti-coloring agent was not added was discolored by the chlorine bleach, but the added product was not a problem. In addition, the mold resistance was also greatly improved from Grade 1 to Grade 3.

[0028]

Examples 2 to 6 and Comparative Example 2 Polyester was melt-spun, and at this time, antibacterial zeolite particles supporting silver ions were added to the melted polymer so that the concentration in the yarn was 1.5%. Dispersed to make antimicrobial PET fibers (1000 denier / 136 filaments). At that time, 2- (4-thiazole) benzimidazole (T
BZ) was blended by changing the addition amount during melt spinning.

As a substance of dirt, (A) POE (25)
Hardened castor oil trialaurate and (B) Softener Humming (registered trademark) stock solution were applied to the surface of the rolled cheese and allowed to stand for a whole day and night. The sex was evaluated. The results are shown in Table 1.

[0030]

[Table 1]

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Claims (2)

(57) [Claims] 1. A resin molded product in which a silver-based inorganic antibacterial agent and a mercapto group-free (benzazole) / azole compound are kneaded in a resin. 2. A method for preventing coloration of a resin molded article having antibacterial and antifungal properties, which comprises kneading a silver-based inorganic antibacterial agent and a mercapto group-free (benzazole) / azole-based compound into a resin. .