JP2653815B2 - Fiber material containing metal ions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a fibrous material containing metal ions, and more particularly, to seaweed and shellfish attachment suitable for aquaculture, fishing, mooring of a floating structure, and the like. Ropes, nets, fishing nets,
The present invention relates to a fiber material capable of providing a sheet.

[Conventional technology]

Fiber materials used in the oceans, rivers, lakes and marshes, especially ropes and nets used for aquaculture and long-term mooring, need to remove attached organisms at regular intervals. Spending. For this purpose, various attempts have been made to provide a material with less biofouling.

That is, it is conventionally known that metals such as copper and silver have a bactericidal action, and by utilizing this property, a method of directly mixing metal fine powders such as copper and silver to obtain an anti-algal fiber ( JP-A-51-117775), a method of cross-twisting a copper wire with a yarn made of fiber or the like (JP-A-52-127899),
Method of adhering resin containing copper powder to fiber surface
62-162074) and the like.

[Problems to be Solved by the Invention] However, the above-mentioned conventionally known methods have various problems such as lack of metal due to water flow and waves, desorption, or excessive dissolution of metal, Therefore, it has been difficult to exhibit a stable anti-algal effect over a long period of time.

In recent years, a variety of antifouling / algaeproofing agents other than the above-mentioned metals have been provided. The emergence of a possible algae-proof material is strongly desired. However, no anti-algae material that satisfies it has been found at present.

An object of the present invention is to provide a fiber material for underwater use which can exhibit algae-repellent performance stably for a long period of time without polluting the environment and can satisfy mechanical properties as a fiber material.

[Means for solving the problem]

An object of the present invention is to provide a polymer layer for fibers with copper ions and / or
Or a fiber having a cross section in which a fiber polymer layer containing a soluble glass containing at least one compound capable of eluting silver ions is compounded and arranged, and the polymer layer containing the soluble glass is a fiber And the arrangement ratio thereof is 10 to 50% of the total cross-sectional area of the fiber, and the copper ions and / or silver ions are contained in the amount of 0.5% to 20% by weight based on the total fiber weight. This is achieved by a fiber material characterized by being composed of fibers made of

The present inventors have been able to develop a long-term anti-algal property by continuously eluting metal ions in water, and as a result of earnestly studying a substance capable of arbitrarily adjusting the solubility, a copper-containing soluble glass and The present inventors have found that the silver-containing glass has extremely good compatibility with the polymer for fibers and that the above-mentioned object of the present invention can be achieved by being mixed in the polymer.

The fiber material referred to herein is generally a general fiber, but is not limited thereto. Rope, net, woven fabric, knitted fabric, non-woven fabric or composite, mixed, It shall include those stacked.
Further, a fibrous material made in a mesh or lattice shape from the beginning is also included in the fibrous material.

It is more preferable that the copper-containing glass and / or the silver-containing glass be blended at a specific position in the cross section of the fiber and in a specific ratio, and in this case, the fiber itself has excellent algal repellent 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 glass and / or the silver-containing glass is always connected to the surface layer in the cross section of the fiber, and when the glass is present only in the inner layer, The solubility of the metal ions in the glass is significantly inhibited, and the metal ions contained in the glass do not elute, so that the anti-algal effect is not exhibited.

FIG. 1 or FIG. 5 shows an arrangement state of the 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 having a sheath-core structure, in which meltable glass is disposed in a sheath portion 1 and a polymer for fibers is disposed in a core portion 2. FIG. Other side 4
FIG. 3 shows an example in which a fiber glass is disposed in four places 5a to 5d of a circular cross section, and a fiber polymer is disposed in other portions 6 in FIG. And Fig. 5 show the protruding ends 7a to 7-
This is an example in which meltable glass is arranged in 7c, 9a, 9b, and a fiber polymer is arranged in other portions 8, 10.

In this case, it is important that the dissolving glass arrangement ratio to the total cross-sectional area of the fiber is 10 to 50%, and 15 to 50%.
More preferably, it is 35%. If it is less than 10%, effective anti-algal properties cannot be imparted, and if it is more than 50%, the mechanical properties such as the strength of the obtained fiber are insufficient, which is not preferable.

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

The above-mentioned copper compound or silver compound to be added to the soluble glass may be any as long as it becomes a metal ion or a metal ion-forming product (a substance that easily becomes a metal ion) in or after elution from the glass. For example, as a copper compound
Inorganic compounds such as Cu ₂ O, Cu ₂ S, CuO, CuS, copper halide, Cu (OH) ₂ , and CuSO _4, and organic compounds such as copper acetate, copper aminoacetate, and copper formate can be used. Further, as the silver compound, an inorganic compound such as Ag ₂ O, Ag ₂ S, AgNO ₃ , silver halide, Ag ₂ SO ₄ , Ag ₂ CO _3, and an organic compound such as silver acetate, silver oxalate, and silver salicylate are used. Can be. Further, one or two or more of the same or different kinds of the aforementioned compounds may be used in combination. However, CuO, Cu ₂ O or Ag ₂ O is preferably used from the viewpoint of compatibility with glass and the content of metal.

Further, the melting glass containing the metal ion is usually a network-forming oxide such as SiO ₂ , B ₂ O ₃ , P ₂ O ₅ , and Na.
It is composed of a network modifying oxide such as ₂ O, K ₂ O, CaO, MgO, BaO, Al ₂ O ₃ , ZnO, TiO _{2 and the} like, and its solubility can be adjusted by the composition ratio of these oxides. What is necessary is just to select a composition ratio according to algae prevention performance and a performance maintenance period.

The amount of metal ions contained and contained in the fiber may be appropriately selected from the alga resistance, the metal content in the dissolvable glass and the fiber cross-sectional area ratio of the dissolvable glass, the spinnability, etc. , Usually 0.5-20% by weight (based on polymer),
Preferably it is 1 to 10% by weight. When the content is small, the spinning performance is insufficient, and when the content is large, there is a problem in spinnability and the mechanical properties of the obtained fiber are not good.

Fiber material in which soluble glass is blended in the fiber material of the present invention (here, fibers made of fiber polymer)
Is a material that can be used as a fiber material for underwater use, as long as it can mix a soluble glass without any problem. For example, polyamide fibers such as nylon 6,66,46; aramid fibers represented by copolymers with paraphenylene terephthalamide and aromatic ether; polyester fibers represented by polyalkylene terephthalate; wholly aromatic polyester fibers Cellulose fibers such as rayon fibers; polyolefin fibers such as ultra-high molecular weight polyethylene; polyoxymethylene fibers; sulfone fibers such as paraphenylene sulfone and polysulfan; polyether ether ketone fibers;
And the like, and may be used alone or optionally in combination.

The fiber may contain various additives that are usually used for improving productivity or characteristics in a production or processing step of the raw yarn. For example, it may contain a heat stabilizer, an antioxidant, a light stabilizer, a leveling agent, a plasticizer, a thickener, a pigment, a glossing agent, a flame retardant, and the like. Further, a resin or the like may be wiped for the purpose of providing protection, workability, and the like to such an extent that the dissolution of the soluble glass is not adversely affected.

The thickness and shape of the fiber are not particularly limited, and may be selected according to the performance and form required according to the application.
For example, the thickness may be 0.5 to 2000 d, preferably 1 to 1000 d, and the shape may be circular or irregular. Further, either a monofilament or a multifilament may be used.

Examples of uses of the fiber material according to the present invention include fishing nets such as fixed nets, materials for aquaculture, various mooring ropes for marine facilities such as buoys, materials for marine development such as seabed mining, water intake facilities for rivers or lakes, However, the present invention is not limited to these, and may be used for applications other than marine materials utilizing other expected effects, for example, antibacterial effect, deodorant effect and the like.

〔Example〕

 Hereinafter, the present invention will be described in detail with reference to examples.

Example 1. Melting glass A shown in Table 1 (product of Yamamura Glass Co., Ltd.)
Was spun, and a monofilament 880d having a sheath-core structure comprising a nylon 6 polymer containing 30% by weight as a sheath and a non-added nylon 6 polymer as a core was spun. The spinning temperature was 240 ° C., the stretching ratio was 6.6 times, and the area ratio of the sheath was 27%.

The 30 yarns were twisted to form a net having a mesh structure of 5 cm x 5 cm, and immersed in the sea about 1 m below the sea surface from spring to summer, to see the effect of preventing the adhesion of marine organisms. Table 2 shows the strength and elongation of the obtained monofilament and the state of biofouling after 4 months.

The strength and elongation were smaller than those of the yarn containing no soluble glass shown in Comparative Example 1, and almost no adhesion of organisms was observed. .

Comparative Example 1. A nylon 6 monofilament containing no soluble glass was spun according to Example 1, and a bioadhesion test was performed on a net. Although excellent in mechanical properties, 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 content with respect to the fiber weight was the same, to obtain a copper-containing nylon 6 monofilament. Many problems during spinning and poor mechanical properties.

Example 2. Melting glass B shown in Table 1 (product of Yamamura Glass Co., Ltd.)
Was spun from a side-by-side type (see FIG. 2) multifilament 1260d / 42f from a nylon 66 polymer containing 20% by weight of the same. Spout temperature is 305
C., the stretching ratio was 6.8 times, and the area ratio of the soluble glass-containing portion was 15%.

80 of these yarns were plied to form a rope having a diameter of about 5 mm, and the state of adhesion to underwater organisms was tested according to Example 1. Table 2 shows the results. The strong elongation was not particularly problematic, and the antialgal effect was also good.

Example 3. Melting glass C shown in Table 1 (product of Yamamura Glass Co., Ltd.)
Using a nylon 6 polymer containing 5% by weight of the polymer, a monofilament 880d having a sheath-core structure was spun according to Example 1 while changing the area ratio of the sheath, and the state of adhesion of the produced net to the sea was tested. Table 2 shows the results. There was no problem with the mechanical properties of the fiber and the anti-algal effect.

Comparative Examples 3 and 4. In Example 3, fibers having an area ratio of 9% and 52% were prepared and tested in the same manner. As shown in Table 2, when the area ratio is small, the algal control effect is poor, and when the area ratio is too large,
Decreases the mechanical properties of the fiber.

Example 4. Melting glass D shown in Table 1 (product of Yamamura Glass Co., Ltd.)
Was spun into a multifilament 1000d / 48f having a sheath-core structure having a sheath portion of a polyester polymer containing 15% by weight of a non-added polymer. The spinning temperature was 310 ° C., the stretching ratio was 5.2 times, and the area ratio of the sheath was 21%. Using this yarn, weaving into a fabric with a warp and weft density of 28 yarns / inch, about 1 m
It was marine biofouling test analogously ^second sample in Example 1.

As shown in Table 2, there was no problem in any of the mechanical properties and anti-algal properties of the fiber.

[Effect of the Invention] Since the fiber material according to the present invention is configured as described above, various products made using the fiber material according to the present invention have stable algal resistance over a long period of time, and It has excellent properties and can therefore be usefully used for various underwater materials. In addition, since no organic antifouling paint conventionally used in this kind of application field is used, water pollution does not occur.

[Brief description of the drawings]

FIG. 1 is a view showing a cross section of a sheath-core fiber which is one embodiment of the fiber material of the present invention, and FIGS. 2 to 5 show fiber cross sections of another embodiment of the fiber material of the present invention, respectively. FIG. 1, 3, 5a to 5d, 7a to 7c and 9a, 9b, which are indicated by oblique lines in the figure, are fused glass compounded parts, and 2, 4, 6, 8, and 10 are non-fused glass compounded parts.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location A01K 75/00 A01K 75/00 C

Claims (1)

(57) [Claims] 1. A fiber having a cross section in which a fiber polymer layer and a fiber polymer layer containing a soluble glass containing at least one compound capable of eluting copper ions and / or silver ions are combined and arranged. The polymer layer containing the soluble glass is connected to the surface layer of the fiber,
The arrangement ratio is 10 to 50% of the total cross-sectional area of the fiber, and the copper ion and / or silver ion is composed of a fiber containing 0.5% to 20% by weight based on the total fiber weight. And fiber material.