JP2003089927A - Fiber having effect for preventing attachment of marine organism - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber capable of preventing the attachment of marine organisms over a long period, and further to provide a fishery material. SOLUTION: This fiber for the fishery material comprises an aromatic polyester resin containing a pyridine-triphenylborane-based antifouling agent and an aliphatic polyester resin composition. The fishery material includes the fiber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber having very little attachment of aquatic organisms when used in contact with sea water or fresh water for a long period of time.

[0002]

2. Description of the Related Art Textile products used for a long period of time in seawater or freshwater include, for example, fixed nets for fisheries, fish nets for farmed fish and shellfish, etc .; used for mooring nautical buoys, light buoys, buoys, etc. Rope used; There is a pollution control fiber curtain used for civil engineering. These textiles are exposed to various adherent aquatic organisms on their surface during long-term contact with seawater or freshwater.
For example, algae such as sea bream and diatoms, coelenterates such as sea anemones and hydrozoa, sponges such as sea sponges, annelids such as Kasane kanzaku, human kanzaku, Fusokomushi,
Tactile objects such as the horned beetle, arthropods such as the barnacles, protozoa such as the white oyster and the sea urchin, and molluscs such as the mussels and the mussels attach to and inhabit.

Due to the attachment of aquatic organisms, for example, in a fixed net, problems such as net subsidence due to increase in weight, net loss due to increased water flow resistance, net damage due to contact / bending, and damage to captured seafood occur. There is. In the case of cage nets, it becomes a source of oxygen deficiency and parasitic diseases due to the reduced flowability of water, which is a major obstacle.

Stationary nets, aquaculture cages, etc. used in contact with seawater or freshwater are tributyltin oxide, triphenyltin oxide, triphenyltin acetate, triphenyltin acetate, triphenyltin acetate, triphenyltin acetate and triphenyltin acetate as measures to prevent the aquatic organisms from adhering. Organotin compounds such as phenyltin chloride, copper,
A method of applying a coating material containing a metal such as silver, zinc or nickel or a compound thereof, or a nitrogen-sulfur-based or halogen-based organic compound is widely known. However, when treating the antifouling paint, there is a problem that it causes a severe unpleasant odor and an irritating odor caused by the antifouling component itself and the organic solvent and further impairs the health of workers. There is a strong demand for products that have long-lasting effects.

Therefore, the applicant of the present invention, as a means for preventing the above-mentioned harmful effects, is a marine product made of a thermoplastic resin containing pyridine-triphenylborane or a derivative thereof (hereinafter sometimes referred to as an antifouling agent). (Japanese Patent Laid-Open No. 2000-344605). The marine products proposed there have excellent sustainability of the antifouling effect to some extent, but when used in water for a long time, the elution amount of the antifouling agent into water gradually decreases and the antifouling effect is improved. The problem was that it could not be fully expressed.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fiber and a fiber product which can prevent adhesion of aquatic organisms for a long period of time.

[0007]

That is, the present invention provides a fiber comprising a thermoplastic resin composition containing pyridine-triphenylborane or a derivative thereof, wherein the thermoplastic resin composition is an aromatic polyester and a fat. A fiber characterized by being a resin composition mainly composed of a group polyester.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Pyridine-triphenylborane used in the present invention has a structure shown below, but derivatives of the compound can be used in the present invention. Halogen-substituted pyridine-triphenylboranes such as 3-bromopyridine-triphenylborane, 4-methylpyridine-triphenylborane, 4 as described in 321 679.
Examples thereof include lower alkyl-substituted pyridine-triphenylborane such as -ethyl-triphenylborane.

[0009]

[Chemical 1]

The content of such a compound in the thermoplastic resin composition is from 0.1 to 0.1 in consideration of the effect of preventing adhesion of aquatic organisms.
It is preferably in the range of 30% by mass. Even if the content of such a compound is increased, the effect is not improved, and if it is too small, the effect is not exhibited. More preferable content is 3
It is in the range of 10% by mass.

It is important that the thermoplastic resin composition containing the above compound is mainly composed of a resin composition of an aromatic polyester and an aliphatic polyester. In the case of aromatic polyester only, when it is used in water for a long time, when the content of antifouling agent decreases, the amount eluted into water decreases, and the antifouling agent remains in the resin at a high content rate. Although the antifouling effect is not easily exhibited, the inclusion of the compound in a composition with an aliphatic polyester does not impair the physical properties of the matrix resin that constitutes the fiber, and prevents the long-term antifouling in water. It is possible to control the elution property of the soiling agent.

As the aromatic polyester used in the present invention, for example, polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyhexamethylene terephthalate can be used, but it is preferable that the aromatic polyester is diol-modified or acid-modified. Triphenylborane is preferable in terms of thermal stability and abrasion resistance during weaving. Specifically, it is mainly composed of a hexamethylene terephthalate unit composed of terephthalic acid and 1,6-hexanediol. It is preferable to use a modified polyester obtained by copolymerizing a third component such as isophthalic acid in terms of strength, melting point and melt viscosity.

The diol component for modifying the polyester is ethylene glycol, diethylene glycol,
1,4-butanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, polyethylene glycol, polytetramethylene glycol and the like, and the acid component is isophthalic acid, naphthalene-2,6-dicarboxylic acid, phthalate. Acid, α, β- (4-carboxyphenoxy) ethane, 4,4-dicarboxydiphenyl, 5
An aromatic dicarboxylic acid such as sodium sulfoisophthalic acid, or an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, or an ester thereof, and the modification ratio is not particularly limited, but both the acid component and the diol component are 50 mol. It is desirable to use at a ratio of less than%.

The modified polyester has a melting point of 15
0 ° C or less, melt viscosity of 10,000 poise or less (160
C., capillary length 10 mm, capillary diameter 1 mm, shear rate 1000 sec.sup.- ¹ ) are desirable. When the melting point is higher than 150 ° C, it is necessary to apply heat higher than 180 ° C in each step of kneading, spinning, and molding with the above-mentioned antifouling agent by heat melting, whereby the antifouling agent vaporizes or decomposes. Therefore, the antifouling effect of the final product may be reduced. Further, if the melt viscosity is too high, shear heat insulation at 180 ° C. or higher may occur in each step of kneading, spinning, and molding, which may cause vaporization or decomposition of the antifouling agent. Therefore, a more preferable melting point is 140 ° C. or lower, and a melt viscosity is 2000 to 5000.
It is a range of poise.

Some modified polyesters have a high melting point. In this case, polybutene as a melting point depressant,
It is preferable that a medium molecular polymer such as liquid polyester is used in combination and contained in the resin composition. The addition amount of the melting point depressant is not particularly limited as long as the melting point is reduced to 150 ° C. or lower and the melt viscosity is reduced to 10,000 poise or lower. It is preferably contained in a proportion of 20% by mass or less with respect to the modified polyester.

The aliphatic polyester used in the present invention is preferably a polyester which is degradable with time, and examples thereof include poly (α-hydroxy acids) such as polyglycolic acid and polylactic acid, or these. And a copolymer having a main repeating unit element. Moreover, poly (ω-hydroxyalkanoates) such as poly (ε-caprolactone) and poly (β-propiolactone) are further added to poly-3-hydroxypropionate, poly-3-hydroxybutyrate and poly-. 3-hydroxycaprolate, poly-3-hydroxyheptanoate,
Poly (β, such as poly-3-hydroxyoctanoate
-Hydroxyalkanoate), and a copolymer of the repeating unit element constituting these and the repeating unit element constituting poly-3-hydroxyvalerate or poly-4-hydroxybutyrate. Further, as the polyalkylene dicarboxylate composed of a condensate of glycol and dicarboxylic acid, for example, polyethylene oxalate,
Polyethylene succinate, polyethylene adipate,
Polyethylene azelate, polybutylene oxalate,
Polybutylene succinate, polybutylene adipate,
Examples thereof include polybutylene sebacate, polyhexamethylene sebacate, polyneopentyl oxalate, and polyalkylene dicarboxylate copolymers containing these as repeating unit elements. Further, in the present invention, a plurality of resins may be selected from these aliphatic polyesters and mixed and used.

In the above-mentioned thermoplastic resin composition, a compatibilizer, a plasticizer, an ultraviolet absorber, a conductivity improver, a modifier such as a crystallization retarder, and an additive such as a color pigment are appropriately added. Can be included.

Next, the fiber of the present invention and the method for producing a fiber product will be described. First, in order to form fibers by the hot melt extrusion method, a so-called twin-screw kneading extruder is used, and an antifouling agent, an aromatic polyester, an aliphatic polyester, and if necessary, a modifier and an additive are uniformly kneaded. Then, a method of extruding this from a spinning nozzle to form a fiber is desirable. The cross-sectional shape of the fiber may be circular, irregular, or hollow,
It may have a composite shape of a core-sheath type or a bimetal type. Of course, the thermoplastic resin composition containing the antifouling agent must form at least a part of the fiber surface.

Further, in the case of producing a so-called resin-coated yarn in which a thermoplastic resin composition containing an antifouling agent is coated on the core yarn, a method of dissolving the thermoplastic resin composition in a solvent and applying it to the surface of the core yarn However, in the present invention, similarly to the above-mentioned thermoplastic fiber using a biaxial kneader, the raw materials are uniformly kneaded, and the antifouling agent-containing resin composition is formed on the core yarn surface by the melt extrusion coating method. A method of coating and producing a resin-coated yarn is desirable. The material of the core yarn is selected from synthetic fiber, regenerated fiber, natural fiber, metal fiber, glass fiber, carbon fiber, etc.
The softening point or decomposition point is 50 than that of the above compound-containing resin.
It is important that the temperature is higher than ℃. The form of the core yarn is not particularly limited, and monofilaments, multifilaments, staples and the like may be used, and a plied yarn or the like made of these may be used as necessary.

[0020]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The evaluations in the examples are evaluated by the following methods.

A state where aquatic organisms adhere to the fiber The yarn is combined into about 10,000 dtex, which is then twisted (bottom twist S200T / M, top twist Z100T / M) to about 20,000.
We obtained plied yarn of dtex. Using this, make a frog or knot net with a size of 5 cm and attach it to a copper frame of 50 cm x 50 cm.
Suspended at a depth of 1 m in the sea of Shirahama, Wakayama Prefecture, the state of attachment of organisms was observed over time, and the following 5 grades were evaluated. Criterion 5: No attachment of organisms was observed. 4: Approximately 10% of the entire surface of the object was found to have organisms attached. 3: Attachment of organisms was recognized on about 20% of the entire surface of the object. 2: Approximately 50% of the entire surface of the object was found to have organisms attached. 1: Adhesion of organisms was found on the entire surface of the object.

Example 1 Modified polyhexamethylene terephthalate (PHMT) copolymerized with 10 mol% of isophthalic acid as an aromatic polyester
58% by mass, as an aliphatic polyester, molecular weight 5 ×
10 ⁴ poly ε-caprolactone (manufactured by Daicel Chemical Industries:
Praxel H5: registered trademark, PCL) 25% by mass, pyridine-triphenylborane 10% by mass, average molecular weight 3
000 polybutene (2000H made by Idemitsu Petrochemical Co., Ltd.)
6% by mass, 0.4% by mass of black pigment made of carbon
Melt-kneaded with a hot-melt resin coating device to obtain 500d
200 parts by mass of the resin composition was coated on 100 parts by mass of polyethylene terephthalate filament (/ manufactured by Kuraray) of / 96f, 120 t / m single twist, and 1500 d of antifouling resin-coated yarn was obtained. As a result of an aquatic organism adhesion test performed on this, a sufficient antifouling effect was exhibited even after 12 months of immersion in the sea.

[0023]

[Table 1]

Example 2 The aliphatic polyester of Example 1 was changed to polybutylene succinate (manufactured by Showa Polymer Co., Ltd .: Bionole # 1000: registered trademark, PBSU) to obtain an antifouling resin-coated yarn. As a result of aquatic organism adhesion test conducted on this, it was immersed in the sea.
It showed a sufficient antifouling effect even after the month.

Example 3 The aliphatic polyester of Example 1 was prepared from the copolymer of 3-hydroxybutyric acid-3-hydroxyvaleric acid having a copolymerization ratio of hydroxyvaleric acid of 12% (manufactured by Zeneca: Biopol D60).
0G: registered trademark, PHB-PHV) was used to obtain an antifouling resin-coated yarn. As a result of an aquatic organism adhesion test performed on this, a sufficient antifouling effect was exhibited even after 12 months of immersion in the sea.

Example 4 The aliphatic polyester of Example 1 was used as a polylactic acid having a D-form of 2% and a number average molecular weight of 70,000 (manufactured by Shimadzu Corporation: Lacty:
A registered trademark, PLA) was used to obtain an antifouling resin-coated yarn.
As a result of an aquatic organism adhesion test performed on this, a sufficient antifouling effect was exhibited even after 12 months of immersion in the sea.

Comparative Example 1 Polyhexamethylene terephthalate modified with 10 mol% of isophthalic acid of aromatic polyester was added to 4,5-dichloro-
2-n-octyl-4-isothiazolin-3-one as 1
0% by mass, 6% by mass of polybutene having an average molecular weight of 3000 (2000H, manufactured by Idemitsu Petrochemical Co., Ltd.), 0.4% by mass of a black pigment made of carbon were contained, and 500 d / 96f was obtained using a hot-melt resin coating device. 120 t / m single twist polyethylene terephthalate filament (made by Kuraray) 10
200 parts by weight of 0 parts by weight was coated to obtain 1500 d of antifouling resin-coated yarn. No aliphatic polyester was added. As a result of an aquatic organism adhesion test conducted on this, the antifouling effect disappeared after 12 months of immersion in the sea.

[0028]

INDUSTRIAL APPLICABILITY The fiber and the fiber product of the present invention are capable of providing a marine product which has no aquatic organisms attached thereto and is safe even when it comes into contact with the human body.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) D02G 3/36 D02G 3/36

Claims (2)

[Claims] 1. A fiber comprising a thermoplastic resin composition containing pyridine-triphenylborane or a derivative thereof, wherein the thermoplastic resin composition comprises an aromatic polyester and an aliphatic polyester as main components. A fiber characterized by being. 2. A marine product containing the fiber according to claim 1.