JPH01213410A - Metallic ion-containing fiber material - Google Patents

Abstract

PURPOSE:To obtain the above fiber material suitable for rope, net, fishing net or sheet suitable for culture, fishing, mooring of floating structure free from adhesion of seaweeds and shellfishes, by blending a fiber material with soluble glass containing a compound capable of eluting copper ion or silver ion. CONSTITUTION:The objective fiber material blended with soluble glass containing at least one compound [e.g., Cu2O, Cu2S, CuO, CuS, copper halide, Cu(OH)2, CuSO4, copper acetate, copper formate, Ag2O, Ag2S, AgNO3, silver halide, Ag2SO4, Ag2CO3, silver acetate, silver oxalate or silver salicylate] capable of eluting copper ion and/or silver ion. The amount of the metallic ion contained is preferably 1-10wt.% (based on the polymer).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a fiber material containing metal ions, and more specifically to a textile material containing seaweeds and shellfish suitable for aquaculture, fishing, mooring of floating structures, etc. This invention relates to fiber materials that can provide ropes, nets, fishing nets, and sheets with less adhesion.

[Conventional technology]

Fiber materials used in the ocean, rivers, lakes, etc., especially for aquaculture,
Ropes, nets, etc. used for long-term mooring require the removal of attached organisms at regular intervals, and a great deal of effort is expended to remove them.

To this end, various attempts have been made to provide materials with less biofouling.

In other words, it has long been known that metals such as copper and silver have bactericidal effects, and by utilizing this property, there is a method to obtain anti-algae fibers by directly mixing fine powders of metals such as copper and silver. (Japanese Unexamined Patent Publication No. 51-117775), ■ Method of intertwisting copper wire with fiber yarn (Japanese Unexamined Patent Publication No. 52-12789)
9), (2) A method of attaching a resin containing copper powder to the fiber surface (Japanese Unexamined Patent Publication No. 162074/1983), etc. have been proposed.

[Problem to be solved by the invention]

However, all of the conventionally known methods described above have various problems such as metal loss or detachment due to water currents and waves, and excessive metal dissolution. It was difficult to express the algae effect.

In addition, in recent years, a large number of various antifouling and algae-proofing agents other than the above-mentioned metals have been provided, but these antifouling and algae-proofing agents have recently come to the fore as environmental problems due to their own water pollution.
Therefore, there is a strong desire for an anti-algae material that can be used safely. However, no anti-algae material has been found that satisfies this requirement.

An object of the present invention is to provide a fiber material for use in water that stably exhibits anti-algae performance over a long period of time without polluting the environment, and also has satisfactory mechanical properties as a fiber material.

[Means to solve the problem]

The object of the invention is achieved by a fiber material blended with a soluble glass containing at least one compound capable of eluting copper and/or silver ions.

The fiber material contains copper ions and/or copper ions in 10 to 50% of the cross-sectional area of the fiber, including at least the surface layer.
Alternatively, it is more preferable that the fiber is made of a fiber on which a soluble glass containing at least one compound capable of eluting silver ions is arranged.

The inventors of the present invention have conducted intensive studies on substances that can exhibit long-term anti-algae properties by continuously eluting metal ions into water, and whose solubility can be arbitrarily adjusted. The inventors have discovered that silver-containing soluble glass has extremely good compatibility with fiber polymers, and that the above-mentioned object of the present invention can be achieved by mixing the silver-containing soluble glass in the polymer, thereby achieving the present invention.

The fiber materials referred to here are usually common fibers, but are not limited to these, and include robes, nets, woven fabrics, knitted fabrics, non-woven fabrics made using these fibers, or composites, mixtures, and laminations thereof. This shall also include those that have been Furthermore, fibrous materials that are originally formed into a net or lattice shape are also included in the fibrous material.

Further, it is more preferable that the copper-containing soluble glass and/or the silver-containing soluble glass are blended at a specific position and in a specific ratio on the cross section of the fiber, and in this way, the fiber itself has excellent anti-algae performance, and A fiber material having mechanical properties suitable for various underwater use materials can be obtained.

In this case, it is necessary that the copper-containing soluble glass and/or the silver-containing soluble glass are always connected to the surface layer in the cross section of the UJT fiber, and if they are present only in the inner layer, , the solubility of metal ions in the glass is significantly inhibited, and the metal ions contained in the glass are not eluted, so that the anti-algae effect is no longer exhibited.

FIG. 1 or FIG. 5 shows the arrangement of soluble glass in a fiber cross section when the fiber material according to the present invention is a fiber. Fig. 1 shows an example of a fiber with a sheath-core structure, in which the sheath part 1 is disposed with soluble glass and the core part 2 is disposed with a polymer for the fiber, and Fig. 2 shows an example in which soluble glass is disposed on one side 3 of the circular cross section. This is an example in which a polymer for fibers is arranged on the other side 4, and FIG. Fourth
Figures 5 and 5 show protruding ends 7 of fibers with irregular cross-sections, respectively.
Melting glass for a to 7c, 9a, 9b, other parts 8
．． This is an example in which a fiber polymer is placed at 10.

In this case, it is preferable that the arrangement ratio of the soluble glass to the total cross-sectional area of the fibers is 10 to 50%. 10%
In the following cases, effective anti-algae properties cannot be imparted, and in cases of 50% or more, the mechanical properties such as strength of the obtained fibers will be insufficient, which is not preferable.

In order to exhibit the anti-algae function for a long period of time, it is necessary to use a compound that can elute copper ions and/or silver ions as the metal in the soluble glass. Compounds that can elute other metal ions cannot exhibit an effective anti-algae effect.

The above-mentioned copper compound or silver compound added to the soluble glass may be any compound that becomes a metal ion or a metal ion-forming substance (substance that easily becomes a metal ion) in the glass or after being eluted from the glass.

For example, copper compounds include Cu2D, Cu2S,
CuO, [:uS.

Copper halide, Cu(0)1)2, Cu5O<
Inorganic compounds such as copper acetate, amine copper acetate, copper formate, and other organic compounds can be used. Examples of silver compounds include Ag2O, Ag2S, AgN0z, silver halide, and Ag25O.

Ag2[:0. Inorganic compounds such as silver acetate, silver oxalate, silver salicylate and the like can be used.

Furthermore, one or more of the same or different types of the aforementioned various compounds may be used in combination. However, from the viewpoint of compatibility with glass and metal content, CuO, Cu2O, or Ag2O is preferably used.

Further, the soluble glass containing metal ions usually has the following properties:
5in2. B20. , P, 05, and network-forming oxides such as Na2O, 20, Can, Mg
O, Ban, A1.0. .

It is composed of network-modifying oxides such as 2nO, Tie, etc., and its solubility can be adjusted by changing the composition ratio of these oxides. The composition ratio may be selected depending on the anti-algae performance and the performance maintenance period.

The amount of metal ions blended and contained in the fiber material may be appropriately selected based on the anti-algae performance, metal content in the soluble glass, fiber cross-sectional area ratio where the soluble glass is blended, spinnability, etc. is usually 0.5 to 20% by weight (based on the polymer), preferably 1 to 10% by weight. If the content is low, the anti-algae performance is insufficient, and if the content is high, problems may occur with spinnability or the mechanical properties of the resulting fibers may be poor.

In the fiber material of the present invention, the fiber material in which soluble glass is blended (here, fibers made of fiber polymer) is a material that can be used as a fiber material for underwater use, and the blending of soluble glass is a problem. It is fine as long as it can be done without any problems. For example, polyamide fibers such as nylon 6.66.46; aramid fibers such as paraphenylene terephthalamide and copolymers with aromatic ether; polyester fibers such as polyalkylene terephthalate; wholly aromatic polyester fibers. ;vinylon fiber;
Cellulose fibers such as rayon fibers; polyolefin fibers such as ultra-high molecular weight polyethylene; polyoxymethylene fibers; sulfone fibers such as paraphenylene sulfone and polysulfone; polyether ether ketone fibers; Just use it.

The fibers may contain various additives that are commonly used to improve productivity or properties in the manufacturing process or processing process of the raw yarn. For example, heat stabilizers, antioxidants,
It may also contain light stabilizers, smoothing agents, plasticizers, thickeners, pigments, brighteners, flame retardants, and the like. Further, it may be coated with a resin or the like for the purpose of protection, imparting workability, etc., to the extent that it does not adversely affect the elution of the soluble glass.

The thickness and shape of the fibers are not particularly limited and may be selected depending on the performance and form required depending on the application. For example, the thickness is 0.5 to 2000 d, preferably 1 to 2000 d.
1000 d, and the shape may be either circular or irregular. Furthermore, either monofilament or multifilament may be used.

Applications of the fiber material of the present invention include fishing nets such as fixed nets, materials for aquaculture, lobes for mooring various marine equipment such as buoys, materials for marine development such as seabed mining, and water intake facilities in rivers or lakes. , etc., but are not limited to these, and have other promising effects, such as antibacterial effects,
It may also be used for purposes other than marine materials, such as those with deodorizing properties.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1゜30 pieces of meltable glass A (Yamamura Glass ■ product) shown in Table-1
A monofilament (monofilament) 880d having a sheath-core structure having a sheath portion containing nylon 6 polymer containing % by weight and a core portion containing additive-free nylon 6 polymer was spun.

The spinneret temperature was 240°C, the stretching ratio was 6.6 times, and the sheath area ratio was 27%.

Thirty of these yarns were twisted together to create a net with a mesh structure of 5 cm x 5 am, and the net was placed about 1 inch below sea level from spring to summer.
The product was immersed in 200 m of seawater to see its effectiveness in preventing the adhesion of marine organisms. Table 2 shows the strength and elongation of the obtained monofilament and the state of bioadhesion after 4 months.

The decrease in strength and elongation was less than that of the soluble glass-free yarn shown in Comparative Example 1, and the attachment of living organisms was hardly tolerated. .

Comparative Example 1 According to Example 1, nylon 6 monofilament containing no soluble glass was spun, and a biofouling test was conducted on a net. Although the mechanical properties were excellent, significant biofouling was observed.

Comparative Example 2 Using the same nylon 6 polymer as in Example 1, CuO was uniformly added so that the copper-containing type with respect to the fiber weight was the same, to obtain a copper-containing nylon 6 monofilament. There are many troubles during spinning, and the R holding property is not good.

Example 2 20 pieces of meltable glass B (Yamamura Glass @ product) shown in Table-1
A side-by-side multifilament (see FIG. 2) of 1260 d/42 f was spun from a nylon 66 polymer containing % by weight and the same polymer without additives. The spinneret temperature was 305°C, the drawing ratio was 6.8 times, the area ratio of the soluble glass-containing part was 15%, and 80 raw yarns of the jaw were twisted together to create a rope with a diameter of about 5 mm. The adhesion state of marine organisms was tested according to Example 1. The results are shown in Table-2.

There were no particular problems with the strength and elongation, and the anti-algae effect was also good.

Example 3 5 pieces of meltable glass C shown in Table 1 (product of Yamamura Glass Co., Ltd.)
Monofilament 880d having a sheath-core structure was spun according to Example 1 using a nylon 6 polymer containing % by weight and varying the area ratio of the sheath portion, and the resulting net was tested for adhesion of marine organisms. The results are shown in Table-2. mechanical properties of fibers,
There was no problem with the anti-algae effect.

Comparative example 3. and 4° In Example 3, fibers with area ratios of 9% and 52% were prepared and tested in the same manner. As shown in Table 2, when the area ratio is small, the algae prevention effect is poor, and when the area ratio is too large,
Decrease the mechanical properties of the fiber.

Example 4 Melting glass D (Yamamura Glass G@preparation product) shown in Table-1 was
A 1000 d/48 f multifilament having a sheath-core structure including a sheath portion containing a polyester polymer containing 5% by weight and a core portion made of an additive-free polymer was spun.

The spinneret temperature was 310°C, the drawing ratio was 5.2 times, and the area ratio of the sheath was 21%. Using this raw yarn, a fabric with a warp and weft density of 28 threads/inch was woven, and a sample of approximately 1 m+ was subjected to a marine organism adhesion test in accordance with Example 1.

As shown in Table 2, there were no problems with either the mechanical properties or antialgae properties of the fibers.

Table-1 Numbers indicate weight percent Table-2 *The state of adhesion was determined visually.

5: Almost no adhesion 4 Slight adhesion 3 Slightly adhesion 2 A lot of adhesion 1 Significant amount of adhesion [Effects of the Invention] Since the fiber material according to the present invention is configured as described above, it is possible to use the fiber material according to the present invention. The various products produced by this method have stable anti-algae properties over a long period of time and have excellent mechanical properties, and therefore can be usefully used in various underwater materials. Furthermore, since the organic antifouling paint conventionally used in this type of application field is not used, water pollution does not occur.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing a cross section of a sheath-core type fiber which is an example of the fiber material of the present invention, and FIGS. 2 to 5 are diagrams showing fiber cross sections of other examples of the fiber material of the present invention. FIG. 1, 3, 5a to 5d, 7a to 7C and 9a, 9b, which are not indicated by hatched areas in the figure, are meltable glass blending parts, 2, 4,
6.8 and 10 are areas without soluble glass. Figure 1 Figure 2 Figure 3 Figure 4 Figure 5

Claims (1)

[Claims] 1. A fiber material blended with soluble glass containing at least one compound capable of eluting copper ions and/or silver ions.