JP2002161427A - Fiber for underwater material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fiber for an underwater material capable of preventing organisms such as algae, shellfishes, etc. from breeding and attaching themselves to the fiber, having an excellent antifouling effect and durability of fiber. SOLUTION: This fiber for an underwater material comprises a nondegradable fiber-forming synthetic polymer containing 0.1-20 mass % of zinc oxide fine particle in which the surface of the particle is coated with a coupling agent and has >=5.0 CN/dtex strength.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an underwater material fiber containing zinc oxide fine particles as an antifouling agent and suitable for fishing nets such as aquaculture nets, stationary nets and mooring ropes.

[0002]

2. Description of the Related Art Since aquaculture nets and fixed nets are used in a state of being immersed in seawater for a long period of time, marine organisms such as algae and shellfish attach to and propagate, and fishes coming from oxygen deficiency due to clogging of the meshes. Growth inhibition and increase in net weight have occurred, which has become a serious problem for fishery personnel.

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

[0004] In addition, the post-treatment method using a paint or the like containing an antifouling agent requires a treatment step, which increases the cost,
Workers may be offended during the process due to the toxicity of the antifouling agent,
There has been a serious problem in terms of safety and health that the working environment has been significantly deteriorated, such as causing headache and dizziness. Not only that,
There is a problem that the antifouling agent falls off with the lapse of use and the durability of the antifouling effect is poor.

In order to solve such a problem, an antifouling fiber mixed with a non-organotin compound-based antifouling agent when producing a fiber from a normal non-degradable polymer is disclosed in Japanese Patent Laid-Open No. 1-17 / 1990.
It is proposed in JP-A-4609 and JP-A-2-182912.
However, the antifouling agents contained in these fibers do not have sufficient antifouling effects, and are particularly inferior in antifouling effects. Algae adherence occurs relatively early in eutrophic seas. There was a problem of doing.

[0006] Further, Canadian Patent Application Publication No. 2044512 discloses a fiber for underwater materials composed of a composition obtained by blending copper or silver ion releasing water-soluble glass with polycaprolactone which is a biodegradable polymer. ing. Since this fiber is composed of a degradable polymer, it is expected that the antifouling agent dissolves well and exhibits an excellent antifouling effect. However, there is a problem that the durability is poor.

Accordingly, the present inventors have developed a composition comprising a non-degradable fiber-forming synthetic polymer as a core component, and a mixture of a non-degradable fiber-forming synthetic polymer and a degradable polymer with an antifouling agent. A fiber for underwater materials composed of a composite fiber having a sheath component has been proposed (JP-A-6-41816). This fiber was excellent in the antifouling effect and the durability of the fibrous material, but a composition in which an antifouling agent was mixed with a mixture of a non-degradable fiber-forming synthetic polymer and a degradable polymer in a sheath component. However, there is a problem in that the operation is complicated and the cost is increased because of using.

[0008]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and both the durability of the antifouling effect and the durability of the yarn physical properties are good and easily obtained. An object of the present invention is to provide a fiber for underwater materials that can be used.

[0009]

Means for Solving the Problems The present inventors have studied to solve the above-mentioned problems, and as a result, have reached the present invention.
That is, the present invention comprises a non-degradable fiber-forming synthetic polymer containing 0.1 to 20% by mass of zinc oxide fine particles whose surface is coated with a coupling agent, and has a strength of 5.
The gist is an underwater material fiber having a CN of 0 CN / dtex or more.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Examples of the non-degradable fiber-forming polymer used in the present invention include polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6, nylon 66, nylon 46, nylon 11, and nylon 12, polyethylene and polypropylene. And polyolefins. These may be appropriately selected and used according to the use, and it is preferable to use polyethylene or nylon 6 as the culture net and use polyethylene terephthalate or nylon 6 as the fixed net.

In the present invention, zinc oxide fine particles whose surfaces are coated with a coupling agent are used as antifouling agents. Zinc oxide fine particles, in addition to the action of ultraviolet absorption and deodorization, has a bactericidal, antibacterial action, but because it has photocatalytic activity when used as it is, it causes photodegradation when contained in resin, There is a disadvantage that the physical properties of the obtained fiber are inferior.

The photocatalytic activity of zinc oxide fine particles is a reaction on the surface of the particles, and attempts have been made to suppress the activity by treating the surface of the particles. For example, a microencapsulated surface treatment for cutting off contact with oxygen or water has been performed, and the zinc oxide fine particles subjected to this treatment optically have the properties of zinc oxide, but have a chemical property. Had the problem of losing the properties of zinc oxide.

Therefore, in the present invention, in order to suppress the photocatalytic activity, which is a drawback of the zinc oxide fine particles, and to have the properties of zinc oxide both optically and chemically, the surfaces of the particles are coupled. The one coated with the agent is used.

The coupling agent is not particularly limited, but a silane coupling agent is preferable. For example, a silane coupling agent KBM-4 manufactured by Shin-Etsu Chemical Co., Ltd.
03, KBM-503.

The coupling agent other than the silane coupling agent includes a coupling agent such as a titanium-based, aluminum-based, zirconium-based, or zircoaluminate-based coupling agent.

The coating amount of the coupling agent depends on the surface area of the zinc oxide fine particles.
It is preferable to set it to about mass%. Since the surface of the zinc oxide fine particles is coated with the coupling agent in this manner, the photocatalytic activity of the zinc oxide fine particles can be sufficiently suppressed without waste with a small amount of coating.
It is possible to maintain the functions of ultraviolet absorption, antibacterial, sterilization, and the like as they are. Therefore, fibers containing zinc oxide fine particles whose surface is coated with such a coupling agent,
Discoloration due to ultraviolet rays is prevented, and at the same time, effects such as antibacterial and sterilizing and antifouling effects are achieved.

Zinc oxide fine particles whose surface is coated with a coupling agent (hereinafter referred to as coated zinc oxide fine particles)
Is preferably 0.1 to 20% by mass, more preferably 5 to 20% by mass, based on the mass of the fiber. When the content is less than 0.1% by mass, there is no antifouling effect. On the other hand, when the content exceeds 20% by mass, yarn breakage occurs in the spinning and drawing steps, and the yarn quality performance is reduced.

The coated zinc oxide fine particles are preferably powders having a particle diameter of 10 μm or less. If the particle diameter is large, there is a problem that a gap is formed in the necking portion at the time of stretching, and there is a problem that cutting occurs at that portion. In addition, the smaller the particle diameter, the larger the surface area and the better the antifouling effect.

The fiber used in the present invention may be a single fiber containing coated zinc oxide fine particles uniformly in the fiber,
A core-sheath type composite fiber mainly containing coated zinc oxide fine particles in a sheath portion may be used. By making the core-sheath type, the coated zinc oxide fine particles can be present on the fiber surface, so that the antifouling effect is sufficiently exhibited, and the content of the coated zinc oxide fine particles can be reduced, thereby further reducing the cost. You can also.

For this reason, when a core-sheath type composite fiber is used,
A core-sheath type filament using a non-degradable fiber-forming synthetic polymer containing no zinc oxide fine particles for the core and a non-degradable fiber-forming synthetic polymer containing zinc oxide fine particles for the sheath component. Is preferred.

When the core-sheath type conjugate fiber is used, the content of the zinc oxide fine particles is preferably 0.1 to 20% by mass in the whole fiber. When the content is less than 0.1% by mass, there is no antifouling effect. On the other hand, when the content exceeds 20% by mass, the content in the sheath component becomes too large, and yarn breakage occurs in the spinning and drawing steps, and the yarn quality is reduced. Performance decreases.

The core / sheath composite mass ratio of the core / sheath composite fiber is preferably from 5/1 to 1/5 from the viewpoint of spinnability, and especially from the viewpoint of fiber strength and antifouling effect. Is preferred.

The cross-sectional shape of the fiber of the present invention is not particularly limited, and the fiber has a circular, elliptical, flat, trilobal, multilobal cross section of four or more leaves, an irregular cross section such as a well, and a four-hole hollow. Such a hollow cross section is exemplified.

Further, the fiber of the present invention may be a monofilament or a multifilament, and has a strength of 5.0 CN / dtex.
That is all. If the strength is less than 5.0 CN / dtex, when used for fishing nets and ropes as underwater materials, the strength is insufficient and the yarn quality performance and durability are poor.

The single fiber fineness of the fiber for underwater materials of the present invention is not particularly limited, but is 0.5 to 2300.
It is preferably 0 dtex.

[0026]

Next, the present invention will be described in detail with reference to examples. In addition, the measurement and evaluation of the value in an Example were performed as follows. <Anti-fouling property> The obtained fiber is twisted into a twisted yarn of about 20,000 denier, and a net of 40 cm x 40 cm is created using this, and attached to a stainless steel frame of 60 cm x 60 cm, and the The animal was suspended underwater at a depth of 1 to 2 m, pulled up after 6, 12, and 18 months, and a suspension test was performed to observe the state of adhesion of living things at that time, and the state of adhesion was evaluated in the following four stages. ：: No adhesion ○: A little adhesion △: About half adhesion ×: Adhesion all over <Strength> Tensile strength was measured according to JIS L 1013 (1981).

Examples 1-4 Relative viscosity (96% sulfuric acid as solvent, concentration 1 CN / dl, temperature 25
Zinc oxide fine particles (Z-NOUVE, manufactured by Mitsui Kinzoku Co., Ltd., average particle size 0.2 μm) obtained by coating the surface of particles with a silane coupling agent on nylon 6 (N6) having a particle size of 3.4 measured at ° C.
m) was kneaded at 40% by mass to obtain a master chip. The master chip and N6 having a relative viscosity of 3.4 were used as the sheath component, and mixed so that the content of the coated zinc oxide fine particles in the sheath portion became the value shown in Table 1. Core component has relative viscosity
N6 of 3.4 was used. Then, the core / sheath composite mass ratio shown in Table 1 was produced as follows. First,
Using an extruder type melt spinning machine, nozzle hole diameter 1.0m
m, using a core-sheath composite spinneret with 4 holes, spinning temperature
It was spun at 275 ° C., cooled in a water bath at 15 ° C. through an air gap, and then taken out at a speed of 20 m / min. Immediately one
The stage uses a 85 ° C hot water bath, and the stretching magnification is 3.0 to 3.5 times.
The second stage was stretched at a total draw ratio of 4.8 to 5.2 times using a non-contact heater at 200 ° C. and 1 m to obtain a core-sheath composite monofilament of 400 denier.

Example 5 The same operation as in Example 1 was carried out except that a monofilament consisting of a single component was used instead of the core-sheath composite fiber, and only the sheath component was used.

Comparative Example 1 The procedure of Example 1 was repeated, except that a master chip containing coated zinc oxide fine particles was not used in the sheath component, and a core-sheath type composite fiber containing no coated zinc oxide fine particles was used.

Comparative Example 2 The same procedure as in Example 1 was carried out, except that the core-sheath composite fiber was not used, and only the sheath component was used to form a monofilament consisting of a single component, and the content of the coated zinc oxide fine particles was 30% by mass. Was.

Table 1 shows the content, strength and antifouling evaluation results of the coated zinc oxide fine particles of the monofilaments obtained in Examples 1 to 5 and Comparative Examples 1 and 2.

[0032]

[Table 1]

Example 6 N6 was used as the core and sheath components as in Example 1 and mixed so that the content of the coated zinc oxide fine particles in the sheath became the value shown in Table 2, and the results are shown in Table 1. The core / sheath composite mass ratio was produced as follows. The mixture was supplied to an extruder-type melt extruder, melted at a spinning temperature of 248 ° C., and discharged from a core-sheath composite spinneret having 24 spinning holes having a hole diameter of 0.3 mm. Cooling air is blown from a cooling device to cool and solidify the yarn, and after applying an oil agent with an oiling roller, the yarn is wound at a winding speed of 4000 m / min and 44 dte.
An x / 24f core-sheath composite multifilament was obtained.

EXAMPLE 7, COMPARATIVE EXAMPLES 3 AND 4 Except that the content of the coated zinc oxide fine particles was as shown in Table 2 except that the sheath component alone was used as a monofilament instead of the core-sheath composite fiber and the sheath component was used. Was performed in the same manner as in Example 6.

Table 2 shows the content, strength and antifouling evaluation results of the coated zinc oxide fine particles of multifilaments obtained in Examples 6 and 7 and Comparative Examples 3 and 4.

[0036]

[Table 2]

As is clear from Tables 1 and 2, Examples 1 to
Both the monofilament obtained in No. 5 and the multifilament obtained in Examples 6 and 7 were excellent in antifouling property, high in strength, and good in spinning property. On the other hand, in Comparative Examples 1 and 3, there was no antifouling effect because no antifouling agent was contained. In Comparative Examples 2 and 4, since the amount of the antifouling agent was too large, the fiber could not be obtained because of poor spinning properties.

[0038]

The fiber of the present invention contains zinc oxide fine particles whose surfaces are coated with a coupling agent as an antifouling agent, so that the fiber has excellent antifouling effect durability and is non-degradable. Since the fiber-forming synthetic polymer is used, the fiber has excellent durability and can be easily obtained.

Continuation of the front page F term (reference) 2B106 AA21 EA02 EA16 HA16 4L035 BB57 BB85 DD14 EE08 EE11 FF02 GG03 JJ05 4L041 AA07 BA21 BA46 BC10 BD02 CA20 CB05 DD01

Claims (2)

[Claims] 1. A non-degradable fiber-forming synthetic polymer containing 0.1 to 20% by mass of zinc oxide fine particles whose surface is coated with a coupling agent, and having a strength of 5.0 CN /
Fiber for underwater materials that is dtex or more. 2. A composite fiber comprising a core component comprising a non-degradable fiber-forming polymer and a sheath component comprising a non-degradable fiber-forming polymer covering the core component, wherein at least the sheath component comprises particles. A fiber for underwater materials, comprising zinc oxide fine particles whose surface is coated with a coupling agent, wherein the content of the zinc oxide fine particles in the whole fiber is 0.1 to 20% by mass and the strength is 5.0 CN / dtex or more.