JPH04126820A - Antimicrobial polyvinyl alcohol-based synthetic fiber and formed product using the same - Google Patents

Abstract

PURPOSE:To obtain the subject fiber, containing a specific amount or more of zeolite-based solid particles supporting metallic ions with germicidal action, having powerful germicidal action, capable of lasting the effects for a long period and useful as filters, cleaning cotton, tissue paper, sanitary materials, etc. CONSTITUTION:The objective fiber containing >=0.05wt.% zeolite-based solid particles supporting metallic ions (preferably Ag<+>, Cu<2+> or Zn<2+>) having germicidal action.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a polyvinyl alcohol (hereinafter abbreviated as PVA) synthetic fiber having excellent bactericidal action and its durability, and a molded article using the same.

<Prior Art> Attempts have been made to incorporate zeolite-based solid particles carrying metal ions having a bactericidal effect into a polymer, and to impart bactericidal ability to fibers, films, etc. made of the polymer.

Conventional attempts have been made mainly with polyester and nylon, but metal ions that have a bactericidal effect are activated in the presence of moisture, so if they are included in these hydrophobic polymers, it is difficult to develop a bactericidal effect. The reality is that it is difficult to do so.

Further, Japanese Patent Application Laid-Open No. 195038/1983 discloses a technique for imparting hydrophilicity to a hydrophobic polyester polymer by incorporating a hydrophilic substance such as polyethylene glycol or sulfonated polystyrene into the polymer.

However, when such fibers and films are used in a wet state for a long period of time, their hydrophilic substances are eluted and they lose their hydrophilicity, resulting in a decrease in their bactericidal effect.

Therefore, there has never been anything in the past that could maintain its effects over a long period of time.

<Problems to be Solved by the Invention> Therefore, the present invention aims to provide a fiber with excellent bactericidal action and its durability, and a molded article using the same.

Means for Solving the Problems> The present inventors have developed a method for producing target fibers and fibers by mixing zeolite solid particles carrying metal ions with bactericidal activity into polymers that are hydrophilic in nature. We thought that it would be possible to obtain a molded product using this method, and after extensive research, we arrived at the present invention.

That is, by selecting a PVA-based polymer as a hydrophilic polymer and adding 0.05% by weight or more of zeolite-based solid particles carrying metal ions with a bactericidal effect to the polymer, the desired fiber can be obtained. It will be done. In addition, the fibers can be used in molded products such as paper and non-woven fabrics with excellent bactericidal action and durability, so that the zeolite solid particles are contained in an amount of 0.05% by weight or more based on the total weight of the molded product. You get something.

In the present invention, the zeolite-based solid particles supporting metal ions having a bactericidal effect are defined as zeolite-based solid particles that carry one or more metal ions having a bactericidal effect on the ion-exchangeable part of a natural or synthetic zeolite made of aluminone liquede. It was retained through exchange.

Ag' is a metal ion with bactericidal action.

Cu'', Zn'° are preferred, and the supported amount is 20% by weight or less in terms of Ag'' relative to the zeolite, Cu2°,
Zn'' is preferably 25% by weight or less.

Furthermore, in order to uniformly support metal ions, the zeolite must have a specific surface area of 150 m'/g or more, and a molar ratio of 5ift/A (ltos) of the constituent components must be 14 or less.

The particle diameter of the zeolite-based solid particles supporting metal ions having a bactericidal effect and added to the PVA-based polymer is 20 μm or less, preferably 10 μm or less, and more preferably 5 μm or less.

On the other hand, the PVA-based polymer is not particularly limited as long as it has a fiber-forming ability of 4-4, and has a degree of polymerization of 500, preferably 1000 or more, and a saponification degree of 88 mol% or more, preferably 95 mol% or more. However, especially when it is desired to impart water resistance to PVA-based fibers, a higher degree of saponification is preferable.

Furthermore, modified PVA copolymerized with carboxylic acid, cationic components, etc. may be used, or a mixture of these and ordinary PvA may be used.

The spinning stock solution contains 0 zeolite solid particles with respect to PVA.
．． Although an aqueous PVA solution containing 0.5% by weight or more is used, PVA may be dissolved in an aqueous dispersion of zeolite solid particles, or conversely, zeolite solid particles may be added to an aqueous PVA solution. The zeolite solid particles must be contained in an amount of 0.05% by weight or more based on the molded product made of PVA fiber alone or a composite of the PVA fiber and other types of fiber, and if it is less than that, the effect is insufficient. .

Such a spinning stock solution may be made into fibers by wet or dry spinning using a known method, followed by roller stretching and mixed heat stretching according to a conventional method, followed by drying, dry heat stretching, and heat treatment as required.

When the post-spinning process is completed by wet heat stretching or drying, the resulting fibers have a low degree of crystallinity and are therefore water-soluble and useful as binder fibers for papermaking.

Further, since the fibers subjected to drawing and heat treatment have a high degree of crystallinity, they can be used as main fibers for paper, and molded products such as nonwoven fabrics can be made from these fibers.

Regarding molded products such as paper and non-woven fabrics using such fibers,
Of course, it is possible to use it by mixing it with other fibrous materials such as bulbs, rayon, polyester, etc., but in order to have a bactericidal effect as a molded product, the zeolite solid particles must be 0.05% of the molded product. It is necessary to adjust the amount of the fiber of the present invention to be used so that the fiber content is at least % by weight.

Furthermore, it is also possible to add a new sterilizing effect to such a molded article by supporting a substance with another function (for example, activated carbon having an adsorption ability).

<Effects of the Invention> The fibers of the present invention and molded products using the same have no sterilization properties because they are kneaded with zeolite-based solid particles that carry metal ions that have a sterilizing effect in PVA, which is a hydrophilic polymer. It has features not found in conventional fibers, such as its strong action and long-lasting effect even after long-term use. Therefore, it can be made into any type of molded product such as fiber, paper, non-woven fabric, net, or knitted fabric, and can be used in a wide range of applications such as filters that require sterilizing power, clean cotton, tissue paper, and impact paper. It can be used for.

<Example> The present invention will be further explained below with reference to Examples.

The bactericidal effect was evaluated by determining the bacterial reduction rate using the shake flask method specified by the Textile Sanitary Processing Council.

The strain used was Staphylococcus aureus II? ” 0 12
732 and E. coli IF03301.

In addition, the bacterial reduction rate was calculated using the following formula.

Bacterial reduction rate = (A - B) / A , Comparing the bacterial reduction rate of unused samples and samples washed with running water at room temperature for 3 months? It was evaluated from this.

In addition, the zeolite solid particles shown in the examples include silver commercially available as Bactekiller A B M 101,
Those each carrying 3.7% by weight of copper were used.

Examples 1 and 2, Comparative Example 1 Bac7 was added to an aqueous solution of completely saponified PVA with a degree of polymerization of 1700.
Kira A B M 101 to 0.07 C Example])
, 2.0 (Example 2), 0.03 (Comparative Example 1) The spinning dope containing 0.03% by weight was wet-spun into a saturated sodium sulfate bath, and subjected to roller stretching, wet heat stretching, drying, and dry heat stretching according to conventional methods. The total stretching ratio is 7 times and the single fiber fineness is 2 denier (d).
fibers were obtained. Table 1 shows the bacteria reduction rate for each fiber.

From this table, it can be seen that Bactegiller is required in an amount of 0.05% by weight or more in the present invention and has an excellent bactericidal effect.

Example 3, Comparative Example 1 1% by weight of Bacte Killer A B M 101 was added to a PVA aqueous solution with a degree of polymerization of 1500 and a degree of saponification of 98 mol%,
A spinning stock solution was prepared, wet-spun in a saturated sodium sulfate bath, roller stretched, wet heat stretched, and dried to obtain water-soluble fibers with a single fiber fineness of 1 d and a melting temperature of 65°C. Pulp using the fiber as a binder fiber for paper making, binder/valve = 8/92
(Example 3), mixed paper at a ratio of 3/97 (Comparative Example 2),
Paper with a tsubo fi of 40 g/m' was obtained.

Table 2 shows the bactericidal content contained in this paper and its bacterial reduction rate.

As shown in Table 2, even in a molded article using the fiber of the present invention, no significant effect is observed when the heptaolide solid particle content is less than 0.05% by weight of the present invention.

Example 4, Comparative Example 3 Twenty-six fibers were obtained in exactly the same manner as in Example 1.2, except that 2.5% by weight of Bactekiller was added to PVA.

(Example 4) In addition, a slurry in which Bacte Killer was dispersed in polyethylene glycol having a molecular weight of 1000 was press-injected into molten polyethylene terephthalate in an amount of 5% by weight, mixed and then spun to obtain a 2D polyester fiber containing 25% by weight of Bacte Killer. I got it. (Comparative example 3) When both are unused and 3
Table 3 shows the bacterial reduction rate after washing with running water.

Table 3 It is clear that the fibers of the present invention have excellent long-lasting bactericidal action.

Furthermore, the weight loss (elution) after 3 months of washing under running water was 0.5% for the fibers of Example 4, which was almost negligible, whereas the fibers of Comparative Example 3
The fiber content is large at 47%, and it is not hard to imagine that most of the polyethylene glycol has been eluted and the hydrophilicity has been lost.

Patent applicant RiRashi Co., Ltd.

Claims (2)

[Claims] (1) Polyvinyl alcohol synthetic fiber containing 0.05% by weight or more of zeolite solid particles carrying metal ions with bactericidal action (2) A molded article consisting of a polyvinyl alcohol synthetic fiber alone or in combination with other types of fibers containing zeolite solid particles carrying metal ions having a bactericidal effect, the polyvinyl alcohol synthetic fiber containing: A molded article made of polyvinyl alcohol-based synthetic fibers containing zeolite solid particles carrying metal ions having a bactericidal effect in an amount of 0.05% by weight or more based on the total weight of the molded article.