JP2003096666A - Fiber material preventing attachment of aquatic organism and having excellent safety - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a marine material capable of preventing attachment of aquatic organisms over a long period and having safety. SOLUTION: A fiber material for the marine material is obtained by coating fibers composed of a thermoplastic resin containing an antifouling agent as a metal salt of bis(2-pyridinethiol-1-oxide) with a biodegradable resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fiber which has very little attachment of aquatic organisms when it is used in contact with seawater or fresh water for a long period of time, and particularly when it is processed or handled as a marine product and is safe. Regarding excellent fiber materials.

[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.

As a means for preventing the above-mentioned harmful effects,
A marine product made of a thermoplastic resin containing a bis (2-pyridinethiol-1-oxide) metal salt (hereinafter also referred to as an antifouling agent) has been proposed. The problem has been improved.

[0006]

DISCLOSURE OF THE INVENTION The object of the present invention is that the human body is more safe than the above-mentioned prior art,
An object of the present invention is to provide a fiber and a fiber product which are durable and can prevent adhesion of aquatic organisms for a long period of time.

[0007]

That is, the present invention comprises a thermoplastic resin component containing a bis (2-pyridinethiol-1-oxide) metal salt and a biodegradable resin component covering the resin component. Is a marine organism attachment-preventing fibrous material, and specifically, the fibrous material comprises a thermoplastic resin component containing a bis (2-pyridinethiol-1-oxide) metal salt as a core component and biodegradation. There is a core-sheath type composite fiber with a resin component as a sheath component and a biodegradable resin component on the outermost surface,
The lower layer is bis (2-pyridinethiol-1-oxide)
A resin-coated yarn in which a thermoplastic resin component containing a metal salt is present and which coats the innermost core yarn.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The bis (2-pyridinethiol-1-oxide) metal salt used in the present invention has a structure shown below, and the metal salt is copper,
Examples thereof include zinc, magnesium, calcium and sodium.

[0009]

[Chemical 1]

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

The thermoplastic resin containing the antifouling agent is not particularly limited, but for example, polyester such as polyethylene terephthalate, polybutylene terephthalate and polyhexamethylene terephthalate can be used. It is preferable to use methylene terephthalate in terms of strength, melting point and melt viscosity. In particular, the modified polyester obtained by copolymerizing modified polyhexamethylene terephthalate with a third component with a diol component or an acid component is used as a modified polyester, because the antifouling agent has thermal stability and abrasion resistance during weaving. It is preferable in terms of sex.

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 over 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. As a result, the antifouling effect of the final product may decrease. 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, a melting point depressant,
A medium molecular weight polymer such as liquid polyester can be used. 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 preferable that the modified polyester is contained in an amount of 20% by mass or less.

The biodegradable resin used in the present invention refers to a resin which is wholly or partially decomposed by organisms, and may be a single resin or a resin mixture. Examples of the biodegradable resin include poly-3-hydroxybutyric acid, 3-hydroxybutyric acid-3-hydroxyvaleric acid copolymer, polyvinyl alcohol, ethylene-modified polyvinyl alcohol, polyγ-
Methyl-L-glutamate, poly ε-caprolactone,
Polyethylene succinate, polybutylene succinate, polylactic acid, polymalic acid, starch, cellulose,
Examples thereof include chitin / chitosan, gluten, gelatin, keratin, collagen and natural rubber. These resins are used as a compound by appropriately mixing them with a non-biodegradable resin such as polyurethane, polymethacrylate, polyethylene, polystyrene, and a dispersant, a plasticizer, a pigment, etc. within a range that does not significantly impair the effects of the present invention. You can also do it.

Next, the method for producing the fiber material of the present invention will be described. To produce a core-sheath type composite fiber having a thermoplastic resin component containing an antifouling agent as a core component and a biodegradable resin as a sheath component, a so-called twin-screw kneading extruder is used, A plastic resin and, if necessary, a modifier and an additive are uniformly melt-kneaded, and the biodegradable resin is melted by another extruder, and these molten polymer streams are combined by a core-sheath type composite spinning device. Then, the biodegradable resin can be extruded from the composite spinning nozzle so as to be a sheath component and made into fibers. The cross-sectional shape of the fiber may be any of circular shape, irregular shape, and hollow type.

In the case of using resin-coated yarn, there is a method of dissolving the thermoplastic resin and the biodegradable resin in a solvent and coating them on the surface of the core yarn. In the present invention, a biaxial kneader is used. Then, the thermoplastic resin containing the antifouling agent is uniformly melt-kneaded, and the core yarn is coated with the antifouling agent-containing thermoplastic resin by the melt extrusion coating method, and then further coated with the biodegradable resin. It can be manufactured.
The material of the core yarn used for the resin-coated yarn is selected from synthetic fiber, recycled fiber, natural fiber, metal fiber, glass fiber, carbon fiber, etc., but the melting point, softening point, or decomposition point contains the antifouling agent described above. It is preferably higher than the resin by 50 ° C. or more. 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.

The method of applying the biodegradable resin to the surface of the fiber material of the present invention is not particularly limited, but when the biodegradable resin compound to be applied is thermoplastic, the core-sheath composite spinning method as described above is used. It is possible to use a technique for producing a resin-coated yarn by a melt coating method or a melt coating method. Further, when the biodegradable resin compound is water-soluble or water-suspendable, fibers or resin-coated yarn made of a thermoplastic resin containing an antifouling agent are dipped and dipped into the biodegradable resin aqueous solution. It can be applied by a nip method. The same applies to a solution dissolved in a solvent or a high-viscosity sol. Further, if a fiber or resin-coated yarn containing an antifouling agent is already processed into a net, mesh or woven form, if a biodegradable resin is applied by the dip and nip method,
The effects of the present invention can of course be achieved. The thickness of the coating layer of the biodegradable resin is not particularly limited, but if it is too thin, it is difficult to spin excessive leaching of the antifouling agent, and therefore it is preferably 1 μm to 100 μm.

In the fiber material of the present invention, the biodegradable resin is present on the surface thereof and entirely covers the resin containing the antifouling agent inside, so that the antifouling agent is excessively applied to the surface of the fiber material. When the fiber material of the present invention is processed or used without exuding, the risk of giving it to hands, arms, etc. is suppressed to a low level. Specifically, the “wiping adhesion amount” obtained by the method described below is 2.5 μm for the fiber material of the present invention.
g / cm ² or less, especially 0.25μg / cm ² or less.
The fiber material of the present invention was subjected to a skin sensitization test using a guinea pig, and as a result, a wiping adhesion amount was 0.2.
Be in the range of 5~2.5μg / cm ^2, risk of skin irritation when the fiber material of the present invention mentioned with bare hands occurs 10-20% risk if 0.25 [mu] g / cm ² or less Was below 10% in the safe area.

[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.

After the fibrous material to be used as a sample for wiping is stored in a thermostatic chamber at 25 ° C. for 30 days, the surface of the fibrous material is white background, thin, and a hand with gloves made of 100% cotton with moderate force. 1 at a speed of about 30 cm / sec
Rub for 5 seconds, shake and extract gloves for 1 hour with methanol, and analyze by high performance liquid chromatography. The amount of the antifouling component present on the yarn surface was converted and quantified from the amount of the antifouling component attached to the gloves. When the sample is in the state of fiber yarn, the main analysis is performed in the state of being wound on a bobbin, and when the sample is in the state of cloth, the fabric is analyzed as it is.

Example 1 Isophthalic acid 10 mol% modified polyhexamethylene terephthalate was added to bis (2-pyridinethiol-1-oxide).
10 mass% of copper salt, 6 mass% of polybutene having an average molecular weight of 3000 (made by Idemitsu Petrochemical Co., Ltd .: 2000H), 0.4 mass% of a black pigment made of carbon were contained, and 500 d was obtained by using a hot-melt resin coating device. / 96f, 120t / m
200 parts by mass of 100 parts by mass of one-sided polyethylene terephthalate filament (manufactured by Kuraray), 15
An antifouling resin-coated yarn of 00d was obtained. The degree of polymerization is 50
0, saponification degree 73 mol%, melt flow rate 5 g / 10
15% by mass of polyvinyl alcohol (manufactured by Kuraray: Poval CP1000) of minutes (210 ° C., load of 2160 g) was applied to the antifouling resin-coated yarn using the same hot-melt resin coating device to prevent biodegradable resin coating. A dirty thread was obtained. An aquatic organism adhesion test was performed on this, and the wiping adhesion amount was measured. From the first month of immersion in the sea, a sufficient antifouling effect was exhibited, and the amount of adhering wiping was 0.08 μg / cm ² , which was a level that was sufficiently satisfactory for safety.

[0024]

[Table 1]

Example 2 The antifouling resin-coated yarn of Example 1 had a molecular weight of 5 × 10 5.^FourPo
Li-caprolactone (manufactured by Daicel Chemical Industries: Praxel)
H5: registered trademark) with a hot-melt resin coating device
The coating was performed in an amount of 0.5% to obtain a biodegradable resin-coated antifouling yarn. this
Aquatic organism adhesion test to determine the amount of wiping adherence
It was measured. Shows antifouling effect from the 1st month of submersion in the sea,
Ping adhesion is 2.52 μg / cm ²And safety is satisfied
It was a good level.

Example 3 Polybutylene succine was added to the antifouling resin-coated yarn of Example 1.
Toh (Showa High Polymer Co., Ltd .: Bionore # 1000: registered trader
20% by mass of the target (PBSU) using a hot-melt resin coating device.
Covered to obtain a biodegradable resin-coated antifouling yarn. About this
Aquatic organism adhesion test to measure the amount of wiping adherence
It was Wiping, showing antifouling effect from the 1st month of immersion in the sea
Adhesion amount is 0.75 μg / cm ²To ensure safety
It was a bell.

Example 4 A 3-hydroxybutyric acid-3-hydroxyvaleric acid copolymer having a hydroxyvaleric acid copolymerization rate of 12% was added to the antifouling resin-coated yarn of Example 1 (manufactured by Zeneca: Biopol D600G, registered. Trademark, PHB-PHV) 20 using a hot melt resin coating device
Mass% coating was performed to obtain a biodegradable resin-coated antifouling yarn. An aquatic organism adhesion test was performed on this, and the wiping adhesion amount was measured. From the first month of immersion in the sea, the antifouling effect was exhibited, and the amount of adhering wiping was 1.83 μg / cm ² , which was a level with satisfactory safety.

Example 5 Starch-modified polyvinyl alcohol polymer alloy (Matterby AF10H, registered trademark, St-PVA, manufactured by Nippon Synthetic Chemical Industry) was applied to the antifouling resin-coated yarn of Example 1 using a hot-melt resin coating device. 20% by mass was coated to obtain a biodegradable resin-coated antifouling yarn. An aquatic organism adhesion test was performed on this, and the wiping adhesion amount was measured. Shows antifouling effect from the 1st month of submersion in the sea, and the wiping adhesion amount is 2.24μg /
The safety was at a level of 2 cm2.

Example 6 10% by weight of polyvinyl alcohol (Kuraray: Kuraray Poval 217) having a degree of polymerization of 1700 and a saponification degree of 88 mol% was added to the antifouling resin-coated yarn of Example 1 and a polyurethane emulsion (Nippon, Nippon Zeon). SX1706, registered trademark, Em) 5% by mass aqueous solution by dipping machine using dipping machine, 5% by mass per dry mass
The coating was performed to obtain a biodegradable resin-coated antifouling yarn. An aquatic organism adhesion test was performed on this, and the wiping adhesion amount was measured. From the first month of submersion in the sea, the antifouling effect was exhibited, and the amount of adhering wiping was 0.23 μg / cm ² , which was a level that was sufficiently satisfactory for safety.

Comparative Example 1 The antifouling resin coated yarn of Example 1 was coated with 20% by mass of a non-biodegradable resin, isophthalic acid 10 mol% modified polyhexamethylene terephthalate, using a hot melt resin coating device. An aquatic organism adhesion test was performed on this, and the wiping adhesion amount was measured. Wiping adhesion is 0.12μg /
Although the safety was satisfactory at cm ^2, it did not show any antifouling effect.

Comparative Example 2 The antifouling resin-coated yarn of Example 1 was subjected to an aquatic organism adhesion test without coating the biodegradable resin, and the wiping adhesion amount was measured. Although the antifouling effect was sufficient, the wiping adhesion amount was 88 μg / cm ² , and the safety was insufficient.

Comparative Example 3 A resin-coated yarn containing no antifouling component was prepared by the method of Example 1, and an aquatic organism adhesion test was conducted to measure the wiping adhesion amount. Vigorous biofouling was observed at the first month of immersion in the sea.

[0033]

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.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2B104 CC28 CG17                 2B106 AA01 AA08 HA13 HA16                 4H011 AD01 BA01 BB09 BB18 DA10                       DD01 DF05 DG05                 4L033 AB02 AC10 BA57 DA02

Claims (4)

[Claims] 1. A marine organism adhesion preventing fiber material comprising a thermoplastic resin component containing a bis (2-pyridinethiol-1-oxide) metal salt and a biodegradable resin component covering the resin component. 2. A core-sheath type composite fiber in which a fiber material has a thermoplastic resin component containing a bis (2-pyridinethiol-1-oxide) metal salt as a core component and a biodegradable resin component as a sheath component. The fiber material according to claim 1. 3. The fiber material is in the form of a resin-coated yarn, a biodegradable resin component is present on the outermost surface of the coating resin layer, and bis (2-pyridinethiol-1-oxide) is present in the lower layer. The fiber material according to claim 1, wherein a thermoplastic resin component containing a metal salt is present and covers the innermost core yarn. 4. A marine product comprising the fiber material according to any one of claims 1 to 3.