JP2786936B2 - Resin-coated yarn with marine organism adhesion prevention effect - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Applications> The present invention relates to ropes, nets, light buoys, mooring buoys,
The present invention relates to a yarn, such as an anti-pollution film, which mainly constitutes a fiber product which comes into contact with seawater for a long period of time, and which has very little adhesion of marine organisms.

<Conventional technology> Textile products such as ropes and nets used in seawater for a long period of time include marine products such as fixed nets for fisheries, moss nets used for livestock and fishery products, and buoys for navigation buoys, light buoys and mooring. For ships, etc.
And civil engineering such as anti-pollution membranes. These fiber products are marine organisms that adhere to the surface while in contact with seawater for a long period of time, for example, algae such as Aosa diatom, coelenterates such as sea anemone, sponges such as sea sponge, and ring animals such as sea squid. Tentacles such as bryozoans, mollusks such as mussels, arthropods such as barnacles, and protocords such as sea squirts attach and inhabit. This can lead to major obstacles such as spills due to seawater, breakage due to contact and bending, and oxygen shortage due to loss of fluidity in seawater and damage to cultured fish and shellfish due to contact.
As a countermeasure for preventing marine organisms from adhering to textile products that come into contact with seawater for a long period of time, the following methods have conventionally been adopted.

First, a method which is generally used as a conventional method is to treat a textile with an organic tin compound such as tributyltin oxide, triphenyltin hydroxide, triphenyltin acetate, or triphenyltin chloride. However, the method of using these drugs has the harmful effects of intense unpleasant odor and pungent odor during the processing work, and in addition, these drugs abnormally accumulate in the body of farmed fish and fish, resulting in malformation and death of fish and shellfish. In recent years, it has been revealed that the harmful effects on the human body that take it are serious, and it has been revealed that the harmful effects on the human body are enormous.

Therefore, there is a demand for a new technology that can replace such an organotin compound having a great adverse effect.

As one of such new technologies, urea compounds and
There is a method of treating textile products with an organic sulfur-nitrogen compound such as a benzimidazole compound, a benzothiazole compound, a thiophthalimide compound, or a sulfonylpyridine compound. This method is based on the fact that organic sulfur-nitrogen compounds have been widely used as pesticides, fungicides and fungicides, and are attempts to use them for marine organisms. In addition, it has been clarified that these compounds are extremely low-toxic to humans and fish, and are further decomposed into completely non-toxic substances after completing the action of preventing the adhesion of marine organisms.

The following method has been proposed as a specific method using an organic sulfur-nitrogen compound having a high stability and a high effect of preventing the adhesion of marine organisms.

For example, as an oil-resin binder, linseed oil, cutting oil, soybean oil, dehydrated castor oil, dry oil such as safflower oil or fish oil, or phenolic resin or oil-resin varnish, the reaction product of polyhydric alcohol and dicarboxylic acid In this method, an alkyd resin or the like is used, and an organic sulfur-nitrogen compound is mixed with the alkyd resin to form a coating material, which is applied to the fiber surface and cured. However, in this method, the fiber becomes hard, so that the workability of twisting, warping, weaving, netting, etc. and the workability such as mounting at the time of use are inferior. It causes inconvenience such as damaging the class. Furthermore, the fatal disadvantage of this method is that although effective when initially put into the sea, the active ingredient and coating resin component elute in a relatively short time due to abrasion etc. due to the weakness of the coating film. Or, it may fall off, and the effect of preventing the adhesion of marine organisms may be lost in a short time.

As described above, a yarn using an organic sulfur-nitrogen compound and having a high marine organism adhesion preventing effect and a sufficient permanent effect has not been obtained until now.

<Problems to be Solved by the Invention> The present invention contains yarns that are extremely excellent as yarns (including fibers) constituting fiber products that come into contact with seawater for a long period of time, that is, containing specific organic sulfur-nitrogen compounds. To provide a yarn with very little shedding and adhesion of marine organisms over a long period of time, with practical strength, form stability and durability, and to provide a particularly excellent organic sulfur-nitrogen compound. Another object of the present invention is to provide a marine organism adhesion preventing yarn which does not make the fiber product too hard.

<Means for Solving the Problems> An object of the present invention is to provide an organic sulfur-nitrogen compound represented by the following general formula [I] or a metal salt or an amine salt complex thereof, which is coated with a resin containing a coating resin. This is achieved by a resin-coated yarn having an effect of preventing marine organisms from adhering.

Wherein Y represents a hydrogen atom, an alkyl group, an alkenyl group or an aralkyl group, R represents a hydrogen atom, a halogen atom or an alkyl group, R 'represents a hydrogen atom, a halogen atom or an alkyl group, and R And R 'may combine to form a benzene ring.

In addition, the yarn referred to here includes a single fiber. That is, a fiber whose surface is coated with the resin is also included.

Preferable specific examples of the organic sulfur nitrogen compound used in the present invention include 2-methyl-4-isothiazoline-3-
on 2-methyl-5-chloro-4-isothiazolin-3-one 1,2-benzisothiazolin-3-one 2-n-octyl-4-isothiazolin-3-one 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one These include zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc acetate, copper chloride, copper bromide, copper nitrate, nickel chloride, calcium chloride, magnesium chloride, iron chloride, manganese chloride, and chloride. It may form a complex compound with sodium, barium chloride, ammonium chloride, other amine chlorides or the like.

The resin-coated yarn referred to in the present invention is preferably a core-sheath resin-coated yarn in which the periphery of the core yarn is sheathed with a thermoplastic synthetic resin, wherein the core yarn is formed from one or more single fibers. And the coating resin is adhered or substantially not adhered to a part of the outer periphery of the single fiber, and the peripheral length ratio of the resin-coated yarn cross section defined below is 1.04 to 1.5. Characterized by being coated with a core yarn.

The coated yarn of the present invention has a substantially constant gap between the core yarn and the coating resin in order to secure the degree of freedom of the core yarn, and the coating resin is a single fiber constituting the core yarn, that is, the single fiber Is a single fiber, the entire circumference of the single fiber is not directly wrapped in direct contact, and if the single fiber is a plurality of two or more, the individual fibers are not wrapped. The fiber is coated so that the entire circumference of the fiber is not wrapped in direct contact.

Having the above-mentioned substantially constant void means that in the cross section of the coated yarn, the circumference ratio defined by `` the inner circumference of the coating resin ÷ the outer circumference of the core yarn '' is 1.04 to 1.5. Means. Here, the outer peripheral length of the core yarn means the inner peripheral length of the coated resin after the coated yarn is heat-treated for at least 3 minutes in a hot air atmosphere at the same temperature as the melt extrusion temperature of the coated resin and the coated resin is re-melted and solidified. Is defined as

As the core yarn constituting the coated yarn of the present invention, a spun yarn, a filament yarn or the like, and a ply-twisted yarn or the like made of these can also be used according to the purpose. Of course, a monofilament yarn may be used. In particular, a twisted yarn or the like having a high convergence of the core yarn often has a cross-sectional structure illustrated in FIG. The material of the core yarn is not particularly limited, such as a natural fiber, a synthetic fiber, and a regenerated fiber, but among them, a material made of a synthetic fiber is particularly desirable in terms of physical properties such as heat resistance and strength.

Here, synthetic fibers are polyester, polyamide,
Polyacrylonitrile-based, polyvinyl alcohol-based, polyvinyl chloride-based, aramid-based, wholly aromatic polyester-based, polyolefin-based, etc., as well as glass fibers, metal fibers, and carbon fibers are included. Above all, the higher the melting point or the decomposition temperature of the yarn, the more preferable the range of resin coating.

The coating resin is selected from thermoplastic synthetic resins, and is selected from polyester, polyamide, polyethylene (including chlorinated polyethylene), polypropylene, urethane, polyacrylate, polyvinyl chloride, polyvinyl alcohol, and polyvinyl alcohol. Vinyl chloride, polyvinylidene fluoride, tetrachloroethylene isoboric compound, ethylene-
A typical example is a vinyl alcohol copolymer, and a mixture of these resins may be used. These resins may also be used as flame retardants, water repellents, conductivity improvers,
A modifier such as an ultraviolet absorber or an additive such as a coloring pigment can be appropriately contained. Further, by containing a sustained-release substance such as a flowable polymer, paraffin, and a surfactant, the organic sulfur-nitrogen compound can be released to the fiber surface for a long period of time, and further excellent antifouling property can be obtained.

The coated yarn obtained in this way has excellent flexibility, excellent handleability, and sufficient strength of the coating layer as compared with those conventionally proposed, and can be used as it is or as twisted rope or string. It can be used alone or as a mixture with other yarns as a combined aggregate. The core yarn is protected by the coating resin from the environment such as abrasion, friction, light, heat, and seawater, and the core yarn is highly modified without modification by selecting the coating resin or adding an antifouling agent to the coating resin. Stain can be effectively and easily provided.

Generally, a resin having a high function and an antifouling agent, a resin in which a large amount of a sustained-release agent is mixed are often remarkably inferior in fiber-forming ability, but according to the present invention, even with such a resin in the presence of a core yarn. The yarn can be easily formed.

Next, a method for producing the above-described coated yarn of the present invention will be described with reference to an example.

The coated yarn of the present invention is preferably produced by a melt extrusion coating method. First, the extrusion temperature of the coated resin is set at least 15 ° C. lower than the melting point or decomposition temperature of the core yarn. The temperature difference during this time
If the temperature is lower than 15 ° C, breakage of the core yarn due to melting deterioration etc. frequently occurs,
Normal coating molding cannot be performed.

The coating resin containing the organic sulfur nitrogen compound and the sustained-release agent in the present invention is guided to a die through a normal screw-type extruder, but in the present invention, the contact between the core yarn and the coating resin is performed outside the die. It is preferable to use a tube type die (FIG. 2 (b)). The tube type die is suitable for creating a gap between the core yarn and the coating resin because the coating resin is not positively pushed into the core yarn. Since there is no risk of resin backflow, the core metal hole diameter is large and the work is easy, and the core thread thickness and shape are excellently adaptable. It has a great advantage in terms of workability, such as being easy to perform and a knot being easily passed.

Conventionally, a pressure-type die (Fig. 2 (a)) is often used to enhance the adhesiveness between the coating resin and the core yarn. However, a flexible and difficult-to-fix core yarn is applied at a high temperature. In this case, the running property and workability of the yarn are actually considerably poor. For example, excessive friction between the cored hole and the core yarn will apply excessive tension to the cored yarn, and the core yarn heated to a high temperature and the core yarn softened by contact with the covering resin will cause extra deformation. Or friction may cause breakage of the single yarn.

However, by controlling the various factors described below, it is not limited to the case of the tube type die,
Even in the case of a pressure type die, a resin-coated yarn having voids can be obtained.

In the method for producing a coated yarn of the present invention, it is preferable that the core yarn travels from the yarn feeding to the winding without practically stretching. Further, it has been found that the circumference ratio is largely determined by the draft rate defined below and the amount of air introduced by the core yarn.

The draft rate is determined by the amount of resin discharged from the die and the running speed of the core yarn. When the draft ratio is large, the coating resin surrounding the core yarn is thinned to reduce the gap between the core yarn and the core yarn. On the other hand, if the amount of air brought in by the core yarn, such as when the traveling speed of the core yarn increases, the gap increases.

In addition to the draft ratio and the core yarn traveling speed, setting and increasing / decreasing the air inside the cored bar (guider) are effective control means upon setting the circumference ratio.

The coated yarn that has been drafted is guided to a cooling zone (water tank) as shown in FIG. 3, where it is cooled and solidified. At the time of cooling and solidifying or / and thereafter, the coated yarn undergoes plastic deformation in the diameter direction of the coated yarn. It is flattened and wound up by the pressure that occurs. At this time, an oil agent may be applied as needed. The pressure may be applied by a nip roll method using two or more rolls or a pressing method against a roll or the like by applying tension. The material of the pressurizer such as a roll is appropriately selected from metal, rubber, and the like. In short, flatness is 1.5
Any method and conditions described above may be used. However, there is a concern that excessive flattening may cause cracking of the coating layer, etc., and such a thing causes exfoliation due to rubbing of the coating layer, etc., and reduces workability. Therefore, the pressure setting for flattening is performed in consideration of this. There is a need. In this flattening step, the coated yarn undergoes the flattening of the cross section and the reduction of the cross sectional area at the same time, and this is also effective for increasing the winding density of the coated yarn.

The wound coated yarn can be heat-treated in a yarn state for the purpose of improving the adhesion of the core yarn to the coating resin, smoothing the surface of the resin, and, if desired, rounding the cross section.

Example 1 Modified polyester (10% by weight of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and 1% by weight of a polyester plasticizer PN-350 manufactured by Adeka Argus Chemical Co., Ltd.) Toa Synthetic COPES-170) was coated with 150 parts by weight of 100 parts by weight of 10 t / m single-twisted yarn and 1000 d / 192f polyester filament using the apparatus shown in FIGS. A resin-coated yarn was obtained.

Example 2 5% by weight of 1,2-benzisothiazolin-3-one
2-n-octyl-4-isothiazolin-3-one is 5
A modified polyester (Toa Gosei COPES-170) containing 1% by weight of a polyester plasticizer PN-350 manufactured by Adeka Argus Chemical Co., Ltd.
10t / m single twist yarn, 1000d / 192f polyester filament 1
150 parts by weight was coated with respect to 00 parts by weight to obtain an antifouling resin-coated yarn.

Example 3 A soft vinyl chloride (molecular weight: 1350) containing 10% by weight of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and 40% by weight of DOP was prepared in the same manner as in Example 1. , 10 t / m single twisted yarn and 100 parts by weight of 1000 d / 192 f polyester filament were coated with 150 parts by weight to obtain an antifouling resin-coated yarn.

Example 4 1,2-Benzisothiazolin-3-one was 5% by weight,
2-n-octyl-4-isothiazolin-3-one is 5
In the same manner as in Example 1, 150 parts by weight of soft vinyl chloride (molecular weight: 1350) blended with 40% by weight of DOP and 100 parts by weight of 10 t / m single-twisted yarn and 100 parts by weight of polyester filament of 1000d / 192f were blended. An antifouling resin-coated yarn was obtained.

Example 5 10% by weight of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and 10% by weight of liquid paraffin
The blended low-density polyethylene was coated in the same manner as in Example 1 by 150 parts by weight with respect to 100 parts by weight of a 10 t / m single-twisted yarn and 1000 d / 192f polyester filament to obtain an antifouling resin-coated yarn.

Example 6 5% by weight of 1,2-benzisothiazolin-3-one
2-n-octyl-4-isothiazolin-3-one is 5
In the same manner as in Example 1, 150 parts by weight of a low-density polyethylene containing 10% by weight of liquid paraffin and 100 parts by weight of a 10 t / m single-twisted yarn and 1000 d / 192f polyester filament were coated. A fouling resin-coated yarn was obtained.

Comparative Example 1 10% by weight of 2- (4-thiazolyl) -benzimidazole, polyester plasticizer manufactured by Adeka Argus Chemical Co.
A modified polyester (Toa Gosei COPES-170) containing 1% by weight of PN-350 was prepared in the same manner as in Example 1,
t / m single twist yarn, 1000d / 192f polyester filament 100
150 parts by weight were coated with respect to parts by weight to obtain an antifouling resin-coated yarn.

Comparative Example 2 Modified polyester containing 10% by weight of 3- (3,4-dichlorophenyl) -1,1-dimethylurea and 1% by weight of a polyester plasticizer PN-350 manufactured by Adeka Argus Chemical Co. (Toa) Synthetic COPES-170) was coated in the same manner as in Example 1 with 150 parts by weight per 100 parts by weight of 10 t / m single twisted yarn and 1000 d / 192f polyester filament to obtain an antifouling resin-coated yarn.

Each of the above-mentioned eight types of fibers was twisted into a rope shape having a diameter of 6.7 mm, and introduced into the Seto Inland Sea in the sea including the summer two seasons (water depth: 1 to 2 m).

After 1, 3, 6, 9, 12, and 18 months, the state of attachment of marine organisms was visually evaluated on a five-point scale. Table 1 shows the results.

From the results shown in Table 1, it is clear that the product of the present invention has an extremely excellent effect of preventing the adhesion of marine organisms and its sustainability.

In the above Examples 1 to 6, the coated yarn obtained was
The coating resin of the core yarn was not very adhered (therefore, it was only partially adhered to the monofilament constituting the core yarn), and all were excellent in flexibility.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of the coated yarn of the present invention, and FIGS. 2 (a) and 2 (b) are cross-sectional views of a main part of a molding die capable of manufacturing the coated yarn of the present invention, and FIG. FIG. 2 is a simplified view of a process capable of producing the coated yarn of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) D06M 13/00-13/535

Claims (2)

(57) [Claims] 1. A resin-coated yarn having a coating layer containing a compound represented by the following general formula [I] or an amine salt complex of a metal salt thereof. Wherein Y represents a hydrogen atom, an alkyl group, an alkenyl group or an aralkyl group, R represents a hydrogen atom, a halogen atom or an alkyl group, R 'represents a hydrogen atom, a halogen atom or an alkyl group, and R And R 'may combine to form a benzene ring. 2. A core-sheath resin-coated yarn in which the periphery of a core yarn is sheathed with a thermoplastic synthetic resin, wherein the core yarn is 1%.
And the coating resin is adhered or substantially not adhered to a part of the outer periphery of the single fiber, and the peripheral length ratio of the resin-coated yarn cross section defined below is
The resin-coated yarn according to claim 1, wherein the core yarn is coated so as to be 1.04 to 1.5.