JPS5826934B2 - Noriami - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved seaweed net suitable for seaweed cultivation.

One of the necessary conditions for the material of the seaweed net is to ensure that the spores (shell spores) released from the seaweed filaments are implanted on the net threads.
It has the ability to prevent implanted spores from falling off.

In particular, if the initial implantation of the shell spores onto the seaweed net threads is insufficient, the subsequent shedding of the young germinated plants will greatly affect growth.

Therefore, the seaweed net material not only has the necessary strength, but also has a boundary layer between the seaweed surface and the seawater that is highly hydrophilic in order to promote complete implantation of the spores onto the seaweed net threads. It is desirable that the material be hard.

In addition to the biological growth factors in seawater, it must also have adequate water retention and water absorption ability when exposed in the air.

This is because when cultivating seaweed, it is customary to expose young seaweed formed on net threads in the air (this is called drying out), and to grow healthy seedlings without suppressing the growth of the growing young. For this reason, drying operations are frequently performed during the budding stage, but it is important to maintain a balance between the degree of drying of the young seaweed and the net threads.

Therefore, nets made of synthetic fibers such as nylon, polypropylene, and polyester have good strength, but because the material is inherently hydrophobic, they do not have the appropriate hydrophilicity and water retention required for attaching and drying out seaweed spores. It is not promising and cannot be put to practical use as a seaweed net.

However, although polyvinyl alcohol fibers have been commonly used as seaweed net materials, these fibers have excessive water absorption and also have shortcomings in terms of strength, so they are not necessarily satisfactory as seaweed net materials. Ta.

There is also the problem of providing nutrients as a condition required for seaweed nets.

In other words, the seedling stage of seaweed cultivation is an important stage that lays the foundation for subsequent growth, and attention must be paid to nutrition in order to raise healthy seedlings.

In order to foster healthy seedlings after the budding stage, the industry has recently devised a system in which small bags with a small amount of fertilizer are dispersed into the sea, allowing the fertilizer to gradually dissolve. Another method is to attach fertilizer to the net by immersing the nori net in a resin liquid mixed with fertilizer.

However, depending on these methods, the leaching of fertilizer content may
It has the disadvantage of concentrating on something over a very short period of time.

In other words, although monospore-attached seaweed nets contain holos whose growth is delayed to varying degrees, if fertilizer content is leached early and concentrated as described above, Before the growth of the hind eyes is promoted, the growth of other large eyes progresses too much, resulting in an undesirable phenomenon in which the growth of the hind eyes is inhibited.

However, as a result of extensive research, the present inventors have found that they can produce nori by using a monofilament obtained by melt-spinning a mixture of a polyamide resin, a saponified long-chain α-olefin-vinyl acetate copolymer, and an anoic acid. If the net is woven into a net, seaweed spores will be able to settle well, and young germinated plants will not fall off.
Even during the drying process, it has an appropriate water retention capacity, so healthy seedlings can be grown well.The mesh body is also strong, and the amino acids, which are nutrients contained in the cultured raw seaweed net, last for a long time. The inventors have discovered that the optimal effect as a seaweed net can be obtained, such as the smooth growth of the hind eyes since it is gradually eluted into seawater, leading to the completion of the present invention.

The seaweed net of the present invention is made of boria resin with a weight coefficient of 50 to 90 and a carbon number of 5.
Water-insoluble α-olefin modified polyvinyl alcohol obtained by saponifying 90 mol or more of the vinyl acetate portion of an α-olefin monovinyl acetate copolymer containing 0.5 to 10 mol of a long-chain α-olefin of ~30 10 to 50 weight φ L - Twisted yarn composed of a monofilament obtained by melt-spinning 0.01 to 5 weight % of three components such as L-tyrosine or the like, or a twisted yarn of the monofilament and a general synthetic fiber. It is made by knitting twisted yarn.

In this case, using polyvinyl alcohol instead of α-olefin-modified polyvinyl alcohol is effective, but it has good melt spinnability, less occurrence of seaweed, excellent growth of seaweed spores, and strong currents. Since it can be used anywhere, the use of α-olefin modified polyvinyl alcohol gives even more favorable results.

In accordance with the present invention, the polyamide resins include nylon 6,
Nylon 66 is used.

α- for α-olefin modified polyvinyl alcohol
As the olefin, a long-chain α-olefin with 5 to 30 carbon atoms is used. If the α-olefin has less than 5 carbon atoms, the molded product obtained will swell too much in water, and polymerization will be inhibited. The disadvantage is that the polymerization operation is complicated because it has to be carried out under pressure;
When an α-olefin exceeding 0 is used, the degree of polymerization decreases and the mechanical properties of the molded product become insufficient.

The copolymerization ratio of such α-olefin needs to be in the range of 0.5 to 10 molar ratio; if it is less than 0.5 molar φ, the molding processability will be poor, and if it exceeds 10 molar φ, the molded product obtained will be poor. The hydrophilicity and water absorption of the material are poor, and the strength is also reduced.

Depending on the type of α-olefin (especially when the number of carbon atoms in the α-olefin is small), the α-
It is desirable that the proportion of the olefin be greater than the above-mentioned lower limit of 0.5 mol φ, and for example, it is preferable that the number of carbon atoms in the α-olefin be n.

Such α-olefins, α-pentene, α-
hexene, α-heptene, α-octene, α-nonene,
α-decene α-dodecene, α-tridecene, α-tetrathecene, α-pentadecene, α-hexadecene, α-octadecene, α-eicosene, etc. may be mentioned, and these may be used alone or in combination of two or more.

When copolymerizing α-olefin and vinyl acetate, other monomers that can be copolymerized with these, such as unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, and maleic acid, or alkyl esters thereof, ethylene, There is no problem even if a small amount of a lower olefin such as propylene, vinyl chloride, acrylonitrile, etc. is present.

The alpha-olefin-vinyl acetate copolymer used is one in which the vinyl acetate portion has been saponified at a mole level of 90 or more.If the vinyl acetate portion is not saponified or if the degree of saponification is less than 90 molar width even if it is saponified, it is hydrophilic. If there is a shortage, seaweed farming becomes unsuitable.

Next, L-tyrosine, which is poorly soluble and has a high melting point, is particularly suitable as the amino acid.

That is, L-tyrosine does not undergo thermal decomposition during melt spinning, and when placed in seawater, it is gradually eluted from the net filament into the water and exhibits an excellent effect on growing healthy seedlings to reach the bud stage.

In addition to the above-mentioned L-tyrosine, examples of amino acids include L-isoleucine, L-leucine, L-methionine,
L-phenylalanine, L-valine, etc. are also used.

The blending proportions of the polyamide resin, α-olefin modified polyvinyl alcohol, and amino acid are selected from the ranges of 50 to 90 weight parts, 10 to 50 weight parts, and 0.01 to 5 weight parts, respectively.

When the proportion of boria-dos resin is higher than this range and the proportion of α-olefin-modified polyvinyl alcohol is lower than this range, hydrophilicity and water absorption are insufficient, resulting in poor adhesion and growth of seaweed spores, while polyamide resin If the ratio of α-olefin-modified polyvinyl alcohol is lower than this range and the ratio of α-olefin modified polyvinyl alcohol is higher than this range, the resin may partially thermally decompose during melt spinning, and the growth of seaweed spores will also become unsatisfactory.

If the amount of amino acids is not at least 0.01 weight, it will be nutritionally deficient, while if it exceeds 5 weight, it will not be as effective as when it is less than 5 weight, and it will be economically disadvantageous. Therefore, there is no need to use many.

The above three components are melt-spun using an extruder and processed into a monofilament.

The appropriate thickness of the filament is several hundred to several thousand deniers.

A suitable number of monofilaments are twisted together to form a twisted yarn, which is then knitted into a net.

It is also possible to create a post-knitted net by twisting the above-mentioned monofilament or its twisted yarn with other general synthetic fibers such as polyolefin, nylon, polyester, polyacrylonitrile, vinylon, etc. or twisted yarn thereof.

Next, the seaweed net of the present invention will be further explained by giving an example.

Hereinafter, "parts" and "φ" are based on weight unless otherwise specified.

Example 1 80 parts of nylon 6 pellets, 20 parts of α-tothycene-modified polyvinyl alcohol prepared by saponifying 98 mol of the vinyl acetate portion of α-dodecene-vinyl acetate copolymer, and 0.0 parts of L-tyrosine. Mix the two parts;
40% of this was supplied to the extruder and the screw extrusion part temperature was 2.
It was melt-extruded under the conditions of 40° C., a discharge part temperature of 230° C., and 24 holes, and then stretched four times to obtain a monofilament of about 500 denier.

A seaweed net was prepared by knitting a twisted yarn made by twisting 12 parts of three monofilaments together.

The growth rate, spore settlement value, and growth degree of the seaweed net are shown in the table.

Example 2 8 monofilaments and nylon 6021 for Example 1
Eight multifilaments of 0 denier (24 filaments) were first twisted together, three of these were twisted together, and then a knitted net was formed.

The results are shown in the table.

Comparative Example 1 Three pieces of commercially available 500 denier vinylon MA12X were twisted together and then knitted into a net.

The results are shown in the table.

Comparative Example 2 12×3 nylon 6 fibers of 500 denier were twisted together and then knitted into a net.

The results are shown in the table.

As is clear from the table above, the seaweed net of the present invention has a good balance of physical properties, and is far more effective in terms of spore adhesion and growth rate than vinylon seaweed nets and nylon seaweed nets.

- The seaweed net of Comparative Example 1 was immersed in a polyvinyl alcohol resin solution containing nitrogen phosphate potassium nutrients and a melamine hardening agent for 30 minutes at room temperature, and then dried;
The L-tyrosine-containing seaweed net in Example 1 was immersed in the sea, and the residual rate of nutrients was measured over time.
The survival rate of the seaweed net of Comparative Example 1 drastically decreased to 8% in just one day, while the survival rate of the seaweed net of Example 1 was 90% after two days, and 78% after five days. 65 buns later, 15
After a few days, it was found to be 52 excellent, indicating that nutrients were being leached out appropriately.

We also conducted experiments by changing the type of polyamide resin, the type and composition of α-olefin-modified polyvinyl alcohol, and the type of amino acid, and by selecting various proportions of these three commandments. Good results similar to those of Example 1 were obtained within the stated ranges.

Claims (1)

[Claims] 1 Polyamide resin 50-90 weight φ, carbon number 5-3
A water-insoluble α-olefin modified polyvinyl alcohol system obtained by saponifying the vinyl acetate portion of an α-olefin-vinyl acetate copolymer containing 0.5 to 10 moles of long-chain α-olefin of 0.0 to 90 moles or more. Resin 10-50 weight φ and amino acids such as L-tyrosine 0.01-5 weight φ
A seaweed net made by knitting a twisted yarn composed of monofilaments obtained by mixing and melt-spinning the monofilaments, or twisted yarns made by twisting the monofilaments and general synthetic fibers.