JPS5826935B2 - Noriyouami - Google Patents

Description

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

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 factor characteristics in seawater, it is also required to have appropriate water retention and water absorption ability when exposed in the air.

This is because in seaweed farming, it is customary to expose the seaweed young that have 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. Dried-out operations are frequently performed during the budding stage, and it is important to maintain a balance between the degree of drying of the young seaweed and the net thread.

However, it has been known to use monofilament and multifilament of synthetic fibers such as polyolefin and nylon as materials for seaweed netting, but monofilament is too stiff and there is a problem with twisting it into yarn, and multifilament is There is a problem that the manufacturing cost is too high, and regardless of whether monofilament or multifilament is used, the shape of the filament itself is smooth and monotonous, so the adhesion area for seaweed spores is small, and the synthetic material that makes up the filament Since the resin itself has poor hydrophilicity, the spores tend to be less likely to settle on the net threads.

In addition, when vinylon, which is highly hydrophilic among synthetic fibers, is used, the settlement of shell spores is good, but on the other hand, it is easy for green seaweed, which is the enemy of seaweed, to adhere and the growth of microorganisms to progress, and furthermore, in areas with large tidal differences, mud The problem was that there was an increase in the amount of adhesion.

Regarding seaweed nets, it is also necessary to solve the problem of adding nutrients.

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 cultivate healthy seedlings that bloom during the young bud stage, the industry has recently started spraying small bags containing fertilizer into the sea.
As a result, a method has been devised in which the fertilizer is gradually leached out, and another method is to immerse the seaweed net in a resin solution mixed with fertilizer to make the fertilizer adhere to the net. Although these methods are currently in use, they have the disadvantage that the leaching of the fertilizer concentrates 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 intensive research by the present inventors in order to completely overcome these conventional problems, we have found that a polyvinyl alcohol-based resin modified with α-olefin, a polyamide-based resin, a polyolefin-based resin, and an amino acid are mixed and melt-molded. The monofilament can be easily split into a split yarn by simply being beaten or bent, and the area of adhesion of seaweed spores in a net made of twisted yarn made from the split yarn increases significantly by splitting. In addition, the seaweed spores settle on the seaweed very well, there is no shedding of young germinated plants, there is almost no adhesion of green seaweed or the growth of microorganisms, and it has an appropriate water retention capacity even during drying operations. This ensures good growth of healthy seedlings, the strong mesh structure, and the fact that the anoic acid, which is a nutrient contained in the cultured seaweed net, gradually dissolves into seawater over a long period of time. It was discovered that the optimal effects of seaweed netting, such as the smooth growth of the eyes, were achieved, and the present invention was completed.

The seaweed net of the present invention is prepared by saponifying the vinyl acetate portion of an α-olefin-vinyl acetate copolymer containing 0.5 to 10 moles of a long-chain α-olefin having 5 to 30 carbon atoms to 90 moles or more. Obtained water-insoluble α-olefin modified polyvinyl alcohol (a) 5-70 weight polyamide resin 5-75 weight polyolefin resin (c) 25-75 weight thick amino acid (d) 0.01-5 weight φ 4
It is made by knitting a twisted yarn composed of a split yarn made by splitting a monofilament obtained by mixing and melt-molding a precipitate, or a twisted yarn made by twisting the split yarn and a general synthetic fiber.

In this case, using polyvinyl alcohol instead of α-olefin-modified polyvinyl alcohol has some effect, but compared to the case of blending the α-olefin-modified polyvinyl alcohol of the present invention, the melt moldability is inferior, and the It is also inferior in terms of prevention of outbreaks, growth of seaweed spores, and mesh strength.

Furthermore, if any one of the resin components (a), (b), or (c) is missing, fiber splitting will not proceed smoothly and the intended purpose will not be fully achieved.

The α-olefin for α-olefin-modified polyvinyl alcohol (a) is a long-chain α-olefin with 5 to 3 carbon atoms.
If an olefin is used and the number of carbon atoms in the α-olefin is less than 5, the molded product obtained will swell too much in water, and the polymerization operation will be complicated because the polymerization must be carried out under pressure. On the other hand, when an α-olefin having more than 30 carbon atoms is used, the degree of polymerization decreases and the mechanical properties of the molded product become insufficient.

The copolymerization ratio of α-olefin needs to be in the range of 0.5 to 10 mol. If it is less than 0.5 mol φ, the molding processability will be poor, and if it exceeds 10 mol 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.

In this way, Zα-olefin, α-pentene, α-
Hexene, α-heptene, α-octene, α-nonene, α
-decene, α-dodecene, α-tridecene, α-tetradecene, α-pentadecene, α-hexadecene, α-octadecene, α-eicosene, etc., 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, propylene, etc. There is no problem in the presence of small amounts of lower olefins such as, vinyl chloride, acrylonitrile, etc.

The α-olefin-vinyl acetate copolymer used is one whose vinyl acetate portion has been saponified to 90 moles or more, and those that are not saponified or even if saponified, the degree of saponification is 90 moles φ
If it is less than that, the hydrophilicity will be insufficient and it will not be suitable for seaweed cultivation.

Nylon 6, nylon 66, etc. are used as the boria □ resin (b).

As the polyolefin resin (c), in addition to polyethylene and polypropylene, copolymers of ethylene and propylene are used.

Next, as the anoic acid (d), L-
Tyrosine is particularly preferred.

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

In addition to the above-mentioned L-tyrosine, examples of button amino acids that can be used include L-isoleucine, L-leucine, L-methionine, L-phenylalanine, and L-valine.

The blending ratios of α-olefin-modified polyvinyl alcohol (a), polyamide resin (b), polyolefin resin (c), and anoic acid (a) are 5 to 70% by weight, 25 to 75% by weight, and 25 to 75% by weight, respectively. Weight rice cake, selected from the range of 0.01 to 5 weight range.

If the proportions of the resin acids ff1a), (b), and (c) are not within this range, the melting properties, hydrophilicity, and adhesion and growth of seaweed will be poor, making it impossible to fully achieve the intended purpose.

If the weight of amino acids is less than 0.01, there will be nutritional deficiencies, while if the weight exceeds 5 weight, the effect will not be better than if it is less than 5 weight φ, and it will be economically disadvantageous. Therefore, there is no need to use many.

The above four components are melt-molded into a monofilament using an extruder.

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

This filament may be subjected to 11 splitting, but it is preferably drawn at a temperature of 120 to 220°C to as high a magnification as possible, preferably about 3 to 8 times, and then subjected to splitting.

Splitting is easily accomplished by bending the filaments using a splitting machine or by striking the filaments.

An appropriate number of the thus obtained split yarns are twisted together to form a twisted yarn, which is then knitted into a net.

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

Next, the seaweed net of the present invention will be further explained with reference to an example.

The terms "department" and "department" below are based on weight unless otherwise specified.

Example 1 α-dodecene content: 7 lulu An α-dodecene-vinyl acetate copolymer with a saponified vinyl acetate moiety of 98 mol.
24 parts of dodecene-modified polyvinyl alcohol, nylon 6
16 parts, 60 parts of polypropylene and 0.2 parts of L-tyrosine.
The mixture was mixed and fed into a 50 mm extruder, melted and extruded under the conditions of a screw compression part temperature of 240°C, a discharge part temperature of 230'C, and a number of holes of 20, and then stretched 6 times to form a product of approximately 500 mm.
A denier monofilament was obtained.

This monofilament is fed to a splitting machine to give it bending,
Split yarn split by 1 to an average fineness of 20 denier was produced, and 1,000 of the split yarns were twisted together to knit a net to create a seaweed net.

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

Example 2 Eight split threads of the button in Example 1 and eight multifilaments of 210 denier (24 filaments) of nylon 6 were combined and pre-twisted, three of these were twisted together, and then knitted.

The results are shown in the table.

Example 3 α-octadecene content: 9 parts of α-octadecene-modified polyvinyl alcohol obtained by saponifying 99 mol% of the vinyl acetate portion of a multi-α-octadecene-vinyl acetate copolymer;
21 parts of nylon 66, Surlyn A1652 (unsaturated carboxylate modified ethylene copolymer manufactured by DuPont) 70
Example 1 except that a mixture of 1 part and 0.3 parts of L-tyrosine was used.
A drawn filament of approximately 500 denier was obtained in the same manner as above, and this was split.

A net for seaweed was prepared by twisting 1000 of the thus obtained split yarns into a net.

The results are shown in the table.

Comparative example 1 Commercially available 500 denier vinylon fiber 1 I twisted the books together and then knitted them together.

2×3 *Results are shown in the table.

Comparative example 2 500 denier nylon 6 fiber 1 It was twisted together and then knitted.

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 significantly superior to vinylon seaweed nets and nylon seaweed nets in terms of spore settlement and growth rate. be effective.

Among them, the seaweed net of Comparative Example 1 was immersed in a polyvinyl alcohol resin solution containing nitrogen-phosphate-potassium nutrients and a melanin-based hardening agent for 30 minutes at room temperature, and then dried; -Tyrosine-containing seaweed nets were immersed in the sea and the nutrient residual rate was measured over time.
The survival rate of the seaweed net of Comparative Example 1 was drastically reduced to 1 to 8 in just one day, whereas the survival rate of the seaweed net of Example 1 was 2.
86% after 5 days, 70% after 5 days, 51% after 10 days, 1
After 5 days, there were 38 steamed rice cakes, indicating that nutrients were being leached out appropriately.

Claims (1)

[Claims] 1 0.5 to 30 long-chain α-olefins having 5 to 30 carbon atoms
Water-insoluble α-olefin modified polyvinyl alcohol (
a) 5-70 weight φ, polyamide resin (b) 5-7
A twisted yarn composed of a split yarn obtained by splitting a monofilament obtained by melt-molding a mixture of 0 weight factor, a polyolefin resin (c) of 25 to 75 weight factor, and an amino acid (d) of 0.01 to 5 weight factor. Or a seaweed net made by knitting a twisted yarn made by twisting the split yarn and general synthetic fiber.