JPH0641816A - Fiber for underwater material - Google Patents

Abstract

PURPOSE:To obtain fiber for underwater materials, capable of preventing organisms such as algae or shellfishes from propagating and sticking thereto and excellent in antifouling effects and durability of the fiber, CONSTITUTION:The objective fiber for underwater materials is composed of conjugate fiber comprising an undecomposable fiber-forming synthetic polymer as a core component and a composition prepared by blending a mixture of the undecomposable fiber-forming synthetic polymer with a decomposable polymer (e.g. polycaprolactone) with an antifouling agent as a sheath component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fishing net such as an aquaculture net or a stationary net, and a fiber for an underwater material such as a mooring rope.

[0002]

2. Description of the Related Art Since aquaculture nets and set nets are used in a state of being immersed in seawater for a long period of time, aquatic organisms such as algae and shellfish attach to them and propagate, resulting in fish deficiency due to oxygen deficiency due to occlusion of the net. Growth inhibition and net weight increase have become a serious problem for fisheries personnel.

As a countermeasure against this, conventionally, aquaculture nets or stationary nets have been subjected to coating treatment with a paint or composition containing an antifouling agent. As the antifouling agent, an organotin compound such as an oxide, hydroxide, chloride or ester of an organic acid of triphenyltin or trialkyltin is generally used, but the organotin compound has toxicity. However, due to problems such as marine pollution and adverse effects on fish bodies, their use has come to be regulated.

Further, the post-treatment method using a paint containing an antifouling agent requires a treatment step, resulting in high cost and
Workers are offended during the process due to the toxicity of antifouling agents,
There was a major safety and health problem that the work environment was significantly deteriorated, such as headaches and dizziness. Not only that,
There is a problem that the antifouling effect is poor in durability, which prevents the antifouling agent from falling off during use and breeding and adhesion of organisms such as algae and shellfish.

As a solution to such a problem, an antifouling fiber containing a nonorganotin compound antifouling agent in the case of producing a fiber from an ordinary non-degradable polymer is disclosed in Japanese Patent Application Laid-Open No. 1-17.
It is proposed in Japanese Patent Nos. 4609 and 2-182912.
However, these fibers do not have sufficient antifouling effect, probably due to insufficient elution of the antifouling agent, and there was a problem that algae adhered relatively early especially in the sea area where eutrophication was advanced. .

[0006] Canadian Patent Application Publication No. 2044512 discloses a fiber for an underwater material composed of a composition in which copper or silver ion-releasing water-soluble glass is mixed with polycaprolactone which is a microbial degradable polymer. . This fiber is
Since it is composed of degradable polymers, the antifouling agent has good elution properties and is expected to exhibit an excellent antifouling effect.
There was a problem that the strength dropped sharply after 5 months and the durability of the fiber was poor.

The present inventors have made a composite fiber having a core-sheath structure,
A fiber for an underwater material using an ordinary non-degradable polymer as a core component and a degradable polymer with an antifouling agent mixed in a sheath component was previously proposed (Japanese Patent Application No. 3-270060). This fiber is
It exerted an excellent antifouling effect by eluting a certain amount or more of the antifouling agent, and it also showed an excellent effect on the durability of the fiber, but it decomposes relatively quickly because the sheath component is composed of degradable polymer. It was found that there was a problem with the durability of the antifouling effect.

[0008]

DISCLOSURE OF THE INVENTION The present invention relates to a fiber for an underwater material in which an antifouling agent is mixed during the production of the fiber, and the fiber for the underwater material is excellent in both the antifouling effect durability and the fiber durability. Is to provide.

[0009]

The present invention is to solve the above-mentioned problems, and the gist thereof is to use a non-degradable fiber-forming synthetic polymer as a core component. And a degradable polymer mixture containing a stainproofing agent in the composition as a sheath component.

The present invention will be described in detail below. In the present invention, as the non-degradable fiber-forming polymer for the core component and the sheath component, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6, nylon 66, nylon 46, nylon 11 and nylon 12, polyethylene, Examples include polyolefins such as polypropylene. These are selected and used appropriately according to the application, and polyethylene or nylon 6 is preferable as the aquaculture net, and polyethylene terephthalate or nylon 6 is preferable as the stationary net.

As the antifouling agent used in the present invention, a non-organotin compound based anti-fouling agent having no problem of marine pollution and adverse effects on fish bodies and having heat resistance is used. Specific examples of the antifouling agent include copper powder, cuprous oxide powder, nickel /
Nickel copper powder, manganese powder, which has a copper mixture ratio of 10/90,
Examples include 2-mercaptobenzothiazole zinc, copper dimethyldithiocarbamate, and the like.

The antifouling agent is preferably used as a powder having a particle size of 10 μm or less, preferably 5 μm or less. When the particle size of the antifouling agent is large, there is a problem that voids are formed in the necking portion during stretching, and cutting occurs at that portion.
The smaller the particle size, the larger the surface area and the better the antifouling effect.

Examples of the degradable polymer used in the present invention include aliphatic compounds such as poly-ε-caprolactone, poly-3-hydroxybutyrate / poly-3-hydroxyvalerate copolymer, polyglycolic acid and polylactic acid. Examples thereof include copolymers of polyesters and aliphatic polyesters such as poly-ε-caprolactone and polyamides such as nylon 6. These are decomposed by microorganisms in water, and finally become carbon dioxide and water, so that they do not cause marine pollution or adverse effects on fish bodies.

The fiber using only the decomposable polymer containing the antifouling agent in the sheath component has a high initial elution rate of the antifouling agent, but is poor in antifouling effect durability, but the fiber of the present invention. Since the antifouling agent is blended in the mixture of the non-degradable polymer and the degradable polymer, it is possible to control the elution rate of the antifouling agent, and even after the degradable polymer is completely decomposed. Continuation of antifouling effect is recognized by the antifouling agent contained in the non-degradable polymer. Although the strength of the fiber is slightly reduced,
There is no problem in practical use.

The core / sheath composite weight ratio of the fiber of the present invention is 1/1.
Approximately 5/1 is suitable, and approximately 4/1 is most preferable in terms of fiber strength and antifouling effect. The core / sheath composite weight ratio is 1 /
When it is less than 1, the strength of the fiber is low, and when it is more than 5/1, the antifouling effect becomes small and the composite spinning becomes difficult, which is not preferable in practice.

The composition of the sheath component is preferably 30 to 85% by weight of non-degradable fiber-forming polymer, 10 to 30% by weight of degradable polymer and 5 to 40% by weight of antifouling agent. . And
The ratio of the non-degradable fiber-forming polymer and the degradable polymer in the sheath component is preferably in the range of 6/4 to 9/1 by weight ratio, and if this ratio is too small, the abrasion resistance of the fiber becomes low, On the other hand, if it is too large, the elution rate of the antifouling agent becomes slow and the antifouling effect becomes small. Further, if the content of the antifouling agent with respect to the sheath component is less than 5% by weight, the antifouling effect becomes small, while if it exceeds 40% by weight, it is difficult to knead into the polymer, which is not preferable.

[0017]

EXAMPLES Next, the present invention will be specifically described by way of examples. The antifouling effect was determined by the following suspension test. Suspension test A yarn of about 20000 denier is twisted into a twisted yarn, and a net with a size of 40 cm x 40 cm is made using this and attached to a stainless steel frame with a size of 60 cm x 60 cm.
Suspended at a position of 2 m, pulled up after 6, 12, and 18 months, observed the state of attachment of organisms, and evaluated in the following four stages. ◎: No adhesion ○: A little adhesion △: About half adhesion ×: Adhesion on the entire surface The tensile strength was measured according to JIS L 1013 (1981).

Examples 1 to 4 Nylon 6 (N6) having a relative viscosity of 3.4 measured at a concentration of 1 g / dl and a temperature of 25 ° C. using 96% sulfuric acid as a solvent and ASTM No.E.
Melt index measured according to the method (190 ℃, 2.16kg) of 4.0g / 10min poly-ε-caprolactone (PC
L) was kneaded with 30% by weight of fine copper powder (Cu) having an average particle diameter of 3.79 μm to obtain two types of master chips.
The core component was N6 having a relative viscosity of 3.4, and the sheath component was a mixture of the above two kinds of master chips so as to have the composition shown in Table 1. A core-sheath composite monofilament having a core / sheath composite weight ratio of 4/1 was prepared. It was manufactured as follows. Using an extruder-type melt spinning machine, using a core-sheath composite spinneret with a nozzle hole diameter of 1.0 mm and a number of holes of 4, spinning at a spinning temperature of 275 ° C and cooling in a water bath of 15 ° C through an air gap, At the speed of 20 m / min, immediately draw the first stage using a hot water bath at 85 ° C and draw at a draw ratio of 3.0 to 3.5 times.
Using a non-contact heater at 1 ° C and 1 m, total draw ratio 4.8-
It was drawn at 5.2 times to obtain a 400 denier core-sheath composite monofilament.

Comparative Examples 1 to 3 In Comparative Example 1, the sheath component does not contain PCL, and in Comparative Example 2 (control), the sheath component is PCL and Cu.
A core-sheath composite monofilament was obtained in the same manner as in Examples 1 to 4, except that the core component did not contain N6 and the sheath component did not contain N6.

Table 1 shows the strength and suspension test results of the monofilaments obtained in Examples 1 to 4 and Comparative Examples 1 to 3.

[0021]

[Table 1]

Examples 5 to 6 Linear polyethylene (PE) having a melt index of 1.0 g / 10 min and P having a melt index of 4.0 g / 10 min
30% by weight of Cu with an average particle size of 3.79 μm in each CL
Two types of master chips were obtained by kneading. The core component is PE with a melt index of 1.0 g / 10 min, and the sheath component is the above 2
A master-sheath composite monofilament having a core / sheath composite weight ratio of 4/1 was prepared as follows by mixing different types of master chips so as to have the composition shown in Table 2. Using an extruder type melt spinning machine, using a core-sheath composite spinneret with a nozzle hole diameter of 1.0 mmφ and 4 holes, the spinning temperature is 285 ° C.
After cooling in a water bath at 5 ° C through an air gap, it is drawn at a speed of 10 m / min. Immediately, the first stage uses a hot water bath at 85 ° C, draw ratio 8.0 to 10.0 times, 2 stages Eyes 120
℃, 1m non-contact heater, total draw ratio 9.0-1
It was stretched 0.5 times to obtain a core-sheath composite monofilament of 400 denier.

Comparative Examples 4 to 5 As Comparative Example 4, one containing no PCL in the sheath component, and as Comparative Example 5 (control), PCL and Cu in the sheath component.
A core-sheath composite monofilament was obtained in the same manner as in Examples 5 to 6 using a material not containing.

Table 2 shows the strength and suspension test results of the monofilaments obtained in Examples 5-6 and Comparative Examples 4-5.

[0025]

[Table 2]

Examples 7 to 8 Polyethylene terephthalate (PET) having a relative viscosity of 1.47 measured at a temperature of 20 ° C. and a concentration of 0.5 g / dl and a melt index of 4.0 g, using an equal weight mixture of tetrachloroethane and phenol as a solvent. 30 minutes each of fine cuprous oxide powder (Cu ₂ O) with an average particle size of 0.9 μm in PCL of / 10 min.
Two kinds of master chips were obtained by kneading by weight. The core component is PET having a relative viscosity of 1.47, and the sheath component is a mixture of the above two types of master chips so as to have the composition shown in Table 3, and the core / sheath composite weight ratio is 2/1. The filament was manufactured as follows. Using an extruder type melt spinning machine, using a core-sheath composite spinneret with a nozzle hole diameter of 0.5 mm and a number of holes of 24, spinning at a spinning temperature of 290 ° C., drawing at a speed of 200 m / min, immediately the first stage 90
Using a heating roller at ℃, draw ratio 3.0 to 3.8 times, the second stage
Using a heating roller at 160 ° C., it was drawn at a total draw ratio of 5.0 to 5.4 times to obtain a 250 denier core-sheath composite multifilament.

Comparative Examples 6 to 7 As Comparative Example 6, one containing no PCL in the sheath component, and as Comparative Example 7 (control), PCL and Cu in the sheath component.
_A core-sheath composite multifilament was obtained in the same manner as in Examples 7 to 8 using a material not containing ₂ O.

Table 3 shows the strength and suspension test results of the multifilaments obtained in Examples 7 to 8 and Comparative Examples 6 to 7.

[0029]

[Table 3]

Next, with respect to the yarns obtained in the above-mentioned Examples and Comparative Examples, changes in the elution amount of copper ions with time were examined as follows. 200 ml of water was added to 20 g of a sample cut into a length of 2 cm, the container was sealed, water was replaced every month, and the concentration of copper ions was measured. The concentration of copper ions was measured according to the emission spectroscopy analysis method using inductively coupled plasma according to ICAP-575.
Performed using II. The results are shown in Table 4. (In Table 4, "3 months" means the concentration of copper ions eluted in one month after the lapse of three months, and the same applies hereinafter.)

[0031]

[Table 4]

As is clear from Table 4, by using a non-decomposable polymer and a decomposable polymer (PCL) in combination in the sheath component, copper ions were stably eluted for a long period of time, and
It can be seen that the elution amount can be controlled by changing the mixing ratio of the degradable polymer.

[0033]

The fiber of the present invention uses a mixture of a non-degradable fiber-forming synthetic polymer and a degradable polymer as the sheath component,
Since the antifouling agent is added to this, it has an effect of eluting the antifouling agent stably for a long period of time, and is excellent in durability of the antifouling effect. Further, the fiber of the present invention uses a non-decomposable fiber-forming synthetic polymer as the core component, and therefore has excellent fiber durability.

Claims (2)

[Claims] 1. A composite comprising a non-degradable fiber-forming synthetic polymer as a core component, and a composition comprising a mixture of a non-degradable fiber-forming synthetic polymer and a degradable polymer and an antifouling agent as a sheath component. Fiber for underwater materials made of fiber. 2. The composition of the sheath component is composed of 30 to 85% by weight of non-degradable fiber-forming polymer, 10 to 30% by weight of degradable polymer and 5 to 40% by weight of antifouling agent. The fiber for underwater materials according to Item 1.