JPS5953007B2 - Fiber for marine product adhesion base - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an adhesive base that has excellent adhesion or sprouting properties for seaweed such as seaweed, seaweed, crustaceans such as seaweed, and marine products such as fish eggs and young shellfish. It relates to fibers for use.

Conventionally, natural fibers such as palm and juro were used as materials for seaweed nets, but in recent years polyvinyl alcohol fibers and polyamide fibers have been used because they do not rot even when immersed in seawater and have excellent strength. fibers are used.

Generally, in order to improve the germination state of seaweed, it is thought that it is necessary not only to get wet easily when immersed in water, but also to retain moisture even when exposed above water at low tide.

However, the above-mentioned synthetic fibers are difficult to wet with water and are unsuitable as materials for seaweed nets in their original state, and a resin processing method has been proposed in which a hydrophilic film such as polyvinyl alcohol is formed on the fiber surface.

Such resin processing methods are complicated, and the hydrophilic processing agent may be eluted during underwater cultivation or handling for frozen storage, and the sugar beet processing layer itself may peel off from the fibers. However, the attached young buds are washed away into the sea, which deteriorates the yield and also causes marine pollution.

The present inventors have arrived at the present invention as a result of intensive research into a method for overcoming the drawbacks of synthetic fiber materials and significantly improving the germination state of seaweed.

That is, the present invention is a marine product adhesion base fiber made of a synthetic polymer mixed with a polyoxyalkylene compound having a molecular weight of 1000 to 1000.

Since the fiber of the present invention has excellent hydrophilicity, seaweed,
In addition to having excellent adhesion and sprouting properties for marine products such as crustaceans, fish eggs, and young shellfish, it also has excellent water retention properties, so it can be used especially when the net is exposed above the water due to low tide. It is characterized by the ability to retain sufficient moisture and the growth of seaweed is extremely good.

In addition to its excellent hydrophilic properties, it also has concave portions on its surface, making it difficult for attached young buds to fall off.

Furthermore, since it has excellent hydrophilicity, it can be used for fish reefs etc. with good results.

Specifically, the polyoxyalkylene compound referred to in the present invention includes polyethylene glycol, polypropylene glycol, a block or random copolymer obtained by copolymerizing ethylene oxide and propylene oxide, and a block obtained by addition polymerizing ethylene oxide to polytetramethylene glycol. Polyalkylene glycols such as copolymers, ether compounds of polyalkylene glycols with one or both ends blocked via an ether bond such as phenoxypolyethylene glycol, dimethoxypolyethylene glycol, and lauroxypolyethylene glycol, stearic acid and polyethylene Examples include ester compounds of glycol, ester compounds of phosphoric acid and polyethylene glycol, ester compounds of polyalkylene glycols such as partial alkali metal salts thereof, and mixtures thereof.

It may also be a polyester polyether block copolymer obtained by condensing dicarboxylic acid with glycol or polyalkylene glycol.

These polyoxyalkylene compounds are substantially non-reactive with synthetic polymers and need to be present in the synthetic fiber as a sushi-shaped or spindle-shaped independent phase after fiber formation.

From the viewpoint of being non-reactive and imparting hydrophilicity, the molecular weight of the polyoxyalkylene compound is 1000 or more and 1000 or more.
It is necessary that the molecular weight is 00 or less, but especially when polyester is used as the synthetic polymer, the molecular weight is 3000 or less.
It is appropriate to use the number above, more preferably 6000 or more.

When the polyoxyalkylene compound is 1000 or less,
It is difficult to incorporate into synthetic polymers, and durable parent wood properties cannot be obtained.

Furthermore, when blended into polyester, in the case of a low molecular weight polyoxyalkylene compound, it is copolymerized by transesterification, making it impossible to impart hydrophilicity.

If the molecular weight of the polyoxyalkylene compound exceeds 100,000, it will be easier to blend, but the resulting fiber will have almost no hydrophilicity.

The amount of the polyoxyalkylene compound blended is preferably 0.5% by weight or more and 20% by weight or less, more preferably 2% by weight or more and 15% by weight or less.

When the amount is less than 0.5% by weight, sufficient hydrophilicity cannot be obtained, and when it is more than 20% by weight, the spinning properties deteriorate.

In the present invention, the synthetic polymers to which the polyoxyalkylene compound is blended include polyesters, polyamides, polyacrylics, polyolefins, polyvinyls, etc. Specific examples include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. , polyesters such as cyclohexane dimetatool and terephthalic acid, polyesters such as paraoxyethoxybenzoate, polyamides such as nylon 6, nylon 6.6, polyolefins such as polyethylene, polypropylene, polyacrylonitrile, polyvinyl chloride, polyvinyl alcohol. Alternatively, it may be a copolymer containing these repeating units or a mixture of these polymers.

However, from the viewpoint of manufacturing, durability, effectiveness, etc., polyester is particularly preferred.

Methods for blending a polyoxyalkylene compound into a synthetic polymer include adding the polyoxyalkylene compound at any stage during the synthesis and polymerization process of the synthetic polymer, and adding the polyoxyalkylene compound to the tips of the synthetic polymer. The synthetic polymer and polyoxyalkylene compound are dissolved in an appropriate solvent and then subjected to dry or wet spinning, and the polyoxyalkylene compound is added from any part of the spinning extruder. Yes, but not particularly limited.

The fibers of the present invention are durable and have excellent hydrophilic properties, and when used as a material for seaweed netting, they retain sufficient moisture even when exposed above the sea surface and have the effect of promoting the germination and growth of seaweed. .

Furthermore, in the present invention, when the cross-sectional shape of the fiber is modified to a shape other than round, hydrophilicity and water retention properties are significantly improved,
The germination and growth of seaweed will be extremely good.

The cross section of the fiber is preferably a modified cross section fiber whose cross section deformation ratio (S) is expressed by the following formula.

(However, in the formula, d represents the single fiber denier.) Further, it is particularly preferable that S is 5200/4 or more and 9000/1 or less.

Examples of specific cross-sectional shapes include C-shape, U-shape, star-shape, starfish-shape, S-shape, W-shape, burst hollow shape, etc.
A type, U type, S type, W type, etc. are preferable.

The germination condition of seaweed improves when these irregular cross-section fibers are used. First, the surface area of the fibers containing polyoxyalkylene compounds improves, resulting in improved hydrophilicity and water retention. Second, it is thought that this is because seaweed spores, which are around 10 microns in size, are more likely to adhere to the surface of the mesh threads.

In addition, in the fibers of the present invention, the polyoxyalkylene compound exists as an independent phase, and since the polyoxyalkylene compound is water-soluble or water-dispersible and is eluted from the fiber surface, there is a large number of polyoxyalkylene compounds on the fiber surface. The ease with which concavities are formed is also thought to promote the attachment and growth of seaweed, crustaceans, young shellfish, etc.

Furthermore, C-shaped, U-shaped, S-shaped,
In the case of irregular cross-section fibers such as W-shaped fibers, the opening width of the four parts is 5 microns or more, preferably 10 microns or more, and the depth is 2 microns or more, preferably 5 microns or more, in a germinated state. The improvement is even more remarkable.

The number and size of the surface depressions can be increased by partial elution treatment of the polyoxyalkylene compound present as an independent phase.

In addition to the polyoxyalkylene compound, non-reactive compounds such as water-soluble inorganic salts and organic compounds that are dispersed in the synthetic polymer and can be eluted with the non-solvent of the synthetic polymer may be added at any stage before fiber formation. The number of concave portions can also be increased by blending, performing elution treatment after spinning, or adding a foaming agent to form foamed fibers.

Furthermore, the polyoxyalkylene compound phase or synthetic polymer phase contains nutrients such as nitrogen, phosphorus, potassium, silicic acid, boric acid, amino acids, salts of chitosan, and metals essential for the germination and growth of seaweed such as iron, manganese, and magnesium. Salts may also be added or blended.

In addition, light stabilizers, heat stabilizers, matting agents, dyes and pigments, fluorescent dyes, etc. may be added, and calcium carbonate, silica, alumina, etc. may be added when used as an adhesion base for culturing oysters, etc. By blending, adhesion and growth can be further promoted.

The fibers of the present invention may be filaments or stable, and may be uncrimped or crimped.

The fibers of the present invention may be used alone or appropriately mixed with other ordinary fibers,
or in combination into knitted fabrics, non-woven fabrics, knitted fabrics, ribbons, etc.
It can be used as a seafood attachment group.

The present invention will be explained below with reference to Examples.

Note that parts and % in the examples mean parts by weight and % by weight.

Example 1 9,100 parts of dimethyl terephthalate, 6,350 parts of ethylene glycol, 5 parts of zinc acetate (dihydrate), and 5 parts of antimony trioxide were charged into a transesterification reaction vessel, and the temperature was 150.
The transesterification reaction was carried out at 230°C for 2 hours.

After transferring the reactant to a polycondensation reactor at 230°C, 575 parts of methoxypolyethylene glycol having an average molecular weight of 10,000 was added thereto, and the temperature was raised from 230°C to 280°C over 80 minutes while reducing the pressure of the reaction system. Further, a polycondensation reaction was carried out at 280°C for 60 minutes under reduced pressure of 0.2 mmHg or less.

The intrinsic viscosity of the obtained polymer (measured at 30° C. in a 2 weight ratio of phenol/natrachloroethane-3) was 0.63.

After drying this polymer, it was spun and elongated from a round nozzle using an extruder type spinning machine at a spinning temperature of 290°C to obtain a fiber of 1500 denier/190 filaments.

For comparison, polyethylene terephthalate having an intrinsic viscosity of 0.64 was obtained and fibers were produced in the same manner except that methoxypolyethylene glycol was not added (Comparative Example 1).

In addition, polyester with an intrinsic viscosity of 0.61 was produced in the same manner as in the example, using polyethylene glycol with an average molecular weight of 800 instead of methoxypolyethylene glycol with an average molecular weight of 10,000 in the example, and fibers were made (Comparative Example 2) .

Three pieces of each were twisted together to form a seaweed net.

These two types of seaweed nets were seeded and cultured.

The condition of the young shoots after 5 days was observed under a microscope, and the number of young shoots was determined. The results are shown in Table 1.

The germination condition of the net containing high molecular weight methoxypolyethylene glycol was excellent.

Example 2 Polyethylene terephthalate obtained by polymerization for comparison in Example 1 was spun into a yarn with a C-shaped cross section and an opening width of 10 mm.
When spinning at a spinning temperature of 290°C from an extruder equipped with a nozzle of ~20 microns, phenoxypolyethylene glycol with a molecular weight of 8,500, which is equivalent to 2% of the total polymer, is fed into the middle of the extruder and mixed. A fiber of 800 denier/40 filaments was obtained by spinning and drawing.

Nori net A was made by twisting 4 x 3 of these.

Nori net B was also made from the same irregular cross-section yarn without the addition of a polyoxyalkylene compound.

These and seaweed net C obtained by processing polyvinyl alcohol with citrus oil on ordinary vinylon yarn were seeded, and a young sprout test was conducted in the same manner as in Example 1.

The net made of polyester thread of the present invention had good young buds.

In addition, Example 2 has a larger cross-sectional deformation ratio than Example 1.
showed excellent young budding.

Example 3 Polyethylene glycol with a molecular weight of 20,000 was added to nylon 6 chips in an amount of 5% of the total amount, and spun and drawn using an extruder type spinning machine equipped with a ten-shaped nozzle to form 840 denier/24 filaments. thread (
D) was created.

For comparison, nylon 6 filament (E) without the addition of polyethylene glycol was prepared in the same manner.

A seaweed net was made by twisting 4 x 3 pieces of each seaweed, and a young bud test was conducted in the same manner as in Example 1.

Claims (1)

[Scope of Claims] 1. A fiber for adhesion of marine products, which is made of a synthetic polymer mixed with a polyoxyalkylene compound having a molecular weight of 1,000 or more and 100,000 or less. 2. The fiber for marine product adhesion base according to claim 1, wherein the synthetic polymer is polyester. 3. The fiber for marine product adhesion base according to claim 1 or 2, which is a modified cross-section fiber whose cross-sectional deformation ratio (S) is represented by the following formula. (However, in the formula, d represents the single fiber denier). 4. The fiber for marine product adhesion base according to claim 1, 2 or 3, which has a concave portion on its surface.