JP2954727B2 - Resin-coated fibers, yarns and fiber products having an effect of preventing aquatic organisms from adhering - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber, a yarn, and a fiber product produced therefrom, which have very little adhesion of aquatic organisms when used in contact with seawater or freshwater for a long time.

[0002]

2. Description of the Related Art Textile products used for a long time in seawater or fresh water include, for example, fishery products such as fixed nets for fisheries, moss nets used for farmed fish and shellfish, and moorings for navigation buoys, light buoys, and buoys. Ropes used; anti-pollution fiber membranes used for civil engineering; These textiles are exposed to seawater and fresh water for a long time,
For example, algae such as blue seaweed and diatom, intestinal animals such as sea anemone, sponges such as sea sponge, annelids such as sea squid, tactile objects such as bryozoan, mollusks such as mussels, arthropods such as barnacles, sea squirts and the like. Protozoa attach and inhabit.

[0003] Adhesion of aquatic organisms causes problems such as sinking of the net due to an increase in weight, loss of the net due to increased water flow resistance, breakage of the net due to contact / bending, and damage to the captured fish and shellfish in a fixed net. I have. In addition, in the case of seine nets, in addition to the sinking of nets due to the increase in weight, it will cause major obstacles such as oxygen deficiency due to reduced fluidity of seawater and freshwater, and damage to cultured fish and shellfish by various attached aquatic organisms. Become.

[0004] As a measure for preventing such aquatic organisms from adhering to textiles used in contact with seawater or freshwater for a long period of time, tributyltin oxide, triphenyltin oxide, triphenyltin acetate, triphenyltin oxide and triphenyltin oxide have been used. Methods of treating the above textiles with organotin compounds such as phenyltin chloride have been widely used. However, the use of an organotin compound has a problem in that the treatment environment is inferior accompanied by severe unpleasant odor and pungent odor when treating textile products with the use of the organic tin compound. In addition, abnormal accumulation of organotin compounds in the body of fish and shellfish causes serious problems such as malformation and death of the fish and shellfish. In recent years has been shown to have significant adverse effects. Therefore, the use of textile products treated with an organotin compound has been voluntarily regulated and tends to be banned entirely.

[0005] Therefore, as one of the new technologies which can be substituted for the organotin compounds having the above-mentioned serious problems, urea-based compounds, benzimidazole-based compounds, benzothiazole-based compounds, thiophthalimide-based compounds, sulfonylpyridine-based compounds, etc. Methods of treating textiles with organic compounds containing sulfur and / or nitrogen have been used. According to this method, the above-mentioned organic compound containing sulfur and / or nitrogen, which has low toxicity to living organisms and has been widely used as an agricultural chemical, a fungicide, a fungicide, and the like, is used for preventing marine organisms from adhering. Things.
It has also been found that these organic compounds have extremely low toxicity to the human body and fish, and decompose into non-toxic substances after being used to prevent marine organisms from adhering.

Means for adhering the organic compound containing sulfur and / or nitrogen to the fibers include:
A method of adhering and curing a curable resin paint containing the organic compound on the surface of a fiber has been proposed, and in this case, an alkyd resin, a phenol resin, or the like is used as the curable resin paint. However, in the case of this method, since the fiber becomes hard, twisting, warping, weaving,
Workability in knitting, rope making, and the like is poor, and workability in actual use is reduced. In addition, there is a disadvantage that the captured or raised fish and shellfish are damaged due to the rough fiber surface. Besides, the fatal disadvantage of this method is that
Although effective when initially put into water, the active ingredient and the coating resin component elute or fall off in a relatively short time due to abrasion, etc. It disappears in between.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a fiber which is highly safe against fish and shellfish and the human body, durable without elution or falling off from textiles, and can prevent the attachment of aquatic organisms for a long period of time. , Yarns and textiles. It is a further object of the present invention to provide fibers, yarns and fiber products for preventing aquatic organisms from adhering, which do not cause the fiber surface to become rough or hard and do not cause damage to the captured or raised fish and shellfish. Further, the present invention provides a fiber, yarn and the like which have good workability at the time of twisting, warping, weaving, knitting, rope making and the like, and have good workability in actual use, such as nets and ropes. It also aims to provide textile products manufactured from.

[0008]

As a result of continuing research by the present inventors, the above-mentioned object of the present invention is to coat fibers or yarns with an ethylene-vinyl alcohol copolymer modified with a formylphenol compound. Has been found to be achievable. Accordingly, the present invention is a fiber, a yarn, and a fiber product obtained therefrom, which are coated with an ethylene-vinyl alcohol-based copolymer modified with a formylphenol-based compound.

In the present invention, the ethylene-vinyl alcohol copolymer modified with a formylphenol compound used for coating fibers and yarns has a basic skeleton consisting of an ethylene-vinyl alcohol copolymer, It means that the alcoholic hydroxyl group of the copolymer is modified with a formylphenol compound to form an acetal. Here, the ethylene-vinyl alcohol-based copolymer constituting the basic skeleton may be a non-crosslinked chain-like copolymer, or may be a crosslinked copolymer by an appropriate method as described later.

The ethylene-vinyl alcohol copolymer constituting the basic skeleton has a proportion of a repeating unit composed of ethylene of about 30 to 70 mol%, and the remainder is vinyl alcohol alone or vinyl alcohol and other vinyl monomers. Preferred is a repeating unit consisting of If the proportion of the ethylene unit in the copolymer is less than 30%, the flexibility and moldability of the copolymer will be poor. When the ratio of ethylene units exceeds 70%,
The proportion of the vinyl alcohol unit is inevitably reduced, and as a result, the rate of modification by the formylphenolic compound is reduced, and it becomes difficult to impart the aquatic organism adhesion-preventing property to fibers, yarns and fiber products. From the viewpoint of preventing aquatic organisms from adhering, the proportion of the vinyl alcohol unit in the ethylene-vinyl alcohol copolymer is preferably about 30 to 70 mol%, particularly preferably about 40 to 70 mol%.

The ethylene-vinyl alcohol copolymer can be obtained by saponifying the vinyl acetate portion of the ethylene-vinyl acetate copolymer, in which case the degree of saponification is about 95% or more. Is good. If the degree of saponification is low, not only the crystallinity of the copolymer is lowered and physical properties such as strength are lowered, but also the copolymer is easily softened, which is not preferable because trouble occurs in the processing step. As the ethylene-vinyl alcohol-based copolymer, generally, one having a number average molecular weight of about 5,000 to 15,000 is preferably used.
Ethylene - vinyl alcohol copolymer is commercially available under the trade name Soaru ^R than Corporation under the trade name EVAL ^R from Kuraray and Nippon Synthetic Chemical Industry Co., it is readily available. However, a commercially available copolymer of ethylene and vinyl acetate may be purchased and saponified.

[0012] Examples of the method for producing the ethylene-vinyl acetate copolymer and the ethylene-vinyl alcohol copolymer used in the present invention are as follows. First, after ethylene and vinyl acetate are radically polymerized in a solvent such as methanol in the presence of a radical polymerization catalyst, unreacted monomers are expelled to produce an ethylene-vinyl acetate copolymer.

Then, the acetate group in the ethylene-vinyl acetate copolymer is hydrolyzed with an alkaline compound such as an alkali metal hydroxide or an alkaline earth hydroxide, and saponified to form an ethylene-vinyl alcohol copolymer. rear,
Pellets are formed in water, washed with water, and dried to collect ethylene-vinyl alcohol copolymer pellets.

In order to improve the softening point, heat resistance, hot water resistance, etc. of the ethylene-vinyl alcohol copolymer or its modified product (acetalized product) with a formylphenol compound, the ethylene-vinyl alcohol copolymer is used. May be crosslinked. As a method for crosslinking an ethylene-vinyl alcohol copolymer or an acetalized product thereof, any method known as a method for crosslinking a vinyl alcohol unit-containing copolymer can be employed. Examples of the crosslinking method include divinyl compounds, monoaldehydes represented by formaldehyde, aldehyde compounds such as dialdehydes, crosslinking with organic crosslinking agents such as polyisocyanates such as diisocyanate, crosslinking with inorganic crosslinking agents such as boron compounds, γ-rays. And crosslinking by radiation or light such as electron beams. For example, when performing a cross-linking treatment with dialdehyde, it is preferable to use a strong acid such as sulfuric acid or hydrochloric acid. If unreacted aldehyde remains after the cross-linking treatment, the dyed product may be discolored or the like. Therefore, it is preferable to oxidize with an oxidizing agent to form a carboxylic acid or a salt thereof.

The crosslinking treatment as described above may be performed at any stage before or after coating the fiber or yarn with the ethylene-vinyl alcohol copolymer or its modified formylphenol compound. It is preferable to perform a cross-linking treatment after coating in view of processability, workability, and the like.
Therefore, as described above, the ethylene-vinyl alcohol-based copolymer and the ethylene-vinyl alcohol-based copolymer modified with a formylphenol-based compound according to the present invention include, in addition to those not subjected to the above-described cross-linking treatment, What has been subjected to a crosslinking treatment is also included.

The modification ratio (acetalization ratio) of the ethylene-vinyl alcohol copolymer with the formylphenol compound is about 1.0 to 40 mol based on the number of moles of vinyl alcohol units in the copolymer. %, Particularly 5 to 40 mol%, of the alcoholic hydroxyl group is preferably modified with a formylphenol compound. If the modification ratio of the vinyl alcohol unit by the formylphenolic compound is less than 1.0 mol%, the effect of preventing aquatic organisms from being adhered cannot be exerted. Does not go up. In modifying the ethylene-vinyl alcohol-based copolymer with a formylphenol-based compound, a method similar to a conventionally known method can be employed as a method for acetalizing a polymer containing a vinyl alcohol unit.

As an example of a modification method using a formylphenol compound that can be used in the present invention, that is, an acetalization method, ethylene is added in the presence of a strong acid such as sulfuric acid, formic acid, or hydrochloric acid having a concentration of about 0.05 to 5N. There is a method in which a vinyl alcohol-based copolymer is reacted at about 15 to 135 ° C. using a concentrated solution of a formylphenol-based compound (generally about 0.2 to 500 g / liter) to perform acetalization. Modification of the ethylene-vinyl alcohol-based copolymer with the formylphenol-based compound may be performed at any stage before or after coating the fiber or yarn with the ethylene-vinyl alcohol-based copolymer. It is preferable that the fiber or the yarn is coated with the vinyl alcohol-based copolymer and then modified with a formylphenol-based compound from the viewpoint of processability, processability, and the like.

The term "formylphenol compound" used in the present invention is a general term for phenol compounds having a formyl group (-CHO) directly bonded to a benzene nucleus. it can. One formylphenol compound may be used alone, or two or more formylphenol compounds may be used in combination. As the formylphenol compound used in the present invention, a formylphenol compound represented by the following Chemical Formula 4, Chemical Formula 5, or Chemical Formula 6 is desirable from the viewpoints of handleability, an effect of preventing aquatic organisms from adhering, availability, and the like.

[0019]

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[0020]

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[0021]

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[In the above chemical formulas 4, 5, and 6, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group or a phenyl group.] Formula 4, Formula 5 and Formula 6
In the formylphenolic compound represented by the formula:
Specific examples of ₁ , R ₂ , R ₃ and R ₄ include a hydrogen atom, a halogen atom such as chlorine, bromine, fluorine and iodine, an alkyl group having 1 to 18 carbon atoms or a phenyl group. The groups R ₁ , R ₂ , R ₃ and R ₄ can be the same or different from one another.

Specific examples of the above-mentioned formylphenol compounds include 2-formylphenol, 3-formylphenol, 4-formylphenol, 2-chloro-4-
Formylphenol, 6-chloro-4-formylphenol, 2-bromo-4-formylphenol, 6-bromo-4-formylphenol, 2-methyl-4-formylphenol, 6-methyl-4-formylphenol,
2-ethyl-4-formylphenol, 6-ethyl-4
-Formylphenol, 2-propyl-4-formylphenol, 6-propyl-4-formylphenol,
2,6-dimethyl-4-formylphenol, 2,6-
Diethyl-4-formylphenol, 2,6-dipropyl-4-formylphenol, 2,6-dichloro-4-
Formylphenol, 2-methyl-6-chloro-4-formylphenol, 2-phenyl-4-formylphenol, 6-phenyl-4-formylphenol and the like can be mentioned. These compounds are all known compounds and are available.

Among the above-mentioned formylphenol compounds, 3-formylphenol, 4-formylphenol, 2-chloro-4-formylphenol, 6-chloro-4-formylphenol, 2-methyl-4-formylphenol, 6-methyl-4-formylphenol,
2-ethyl-4-formylphenol, 6-ethyl-4
-Formylphenol, 2,6-dimethyl-4-formylphenol, 2,6-diethyl-4-formylphenol, 2,6-dichloro-4-formylphenol, 2
-Phenyl-4-formylphenol, 6-phenyl-
4-Formylphenol and the like are preferred from the viewpoints of easy reaction with hydroxyl groups in the ethylene-vinyl alcohol copolymer, availability, and an effect of preventing aquatic organisms from adhering.

The fibers and yarns coated with an ethylene-vinyl alcohol copolymer modified with a formylphenol compound include long fibers such as monofilaments, short fibers such as staples, filament yarns, spun yarns, and blends thereof. Any of yarn, blended yarn, ply twisted yarn, etc. may be used. The fibers and yarns may be composed of any of organic or inorganic natural fibers, synthetic fibers, regenerated fibers, artificial fibers and the like.
Among them, organic synthetic fibers; and inorganic fibers such as glass fibers, metal fibers, and carbon fibers are desirable from the viewpoint of physical properties such as heat resistance and strength. Examples of the synthetic fibers in this case include polyester-based, polyamide-based, polyacrylonitrile-based, polyvinyl alcohol-based, polyvinyl chloride-based, aramid-based, wholly aromatic polyester-based, and polyolefin-based synthetic fibers. Temperature range, etc. that can be used when a synthetic fiber having a high melting point or decomposition temperature or a yarn composed of the same is coated with an ethylene-vinyl alcohol copolymer or an ethylene-vinyl alcohol copolymer modified with a formylphenol compound. Is desirable.

The method of providing a coating layer of an ethylene-vinyl alcohol copolymer modified with a formylphenol compound on a fiber or a yarn includes the steps of (i) coating an ethylene-vinyl alcohol copolymer on a fiber or yarn prepared in advance. (Ii) a method of melt-extrusion coating a fiber or a yarn previously produced with an ethylene-vinyl alcohol-based copolymer modified with a formylphenol compound, (i
ii) A melt or solvent solution of the ethylene-vinyl alcohol copolymer is applied to fibers or yarns previously manufactured by an appropriate method, or the fibers or yarns previously manufactured are melted or dissolved in a solvent solution thereof. (Iv) applying a melt or solvent-dissolved solution of an ethylene-vinyl alcohol copolymer modified with a formylphenol compound to a fiber or yarn previously produced by an appropriate method; Or dipping a pre-produced fiber or yarn in their liquid, (v)
A method of forming a layer of an ethylene-vinyl alcohol copolymer at the same time as producing a fiber or yarn (for example, spinning) so as to form a sheath on the outside thereof, followed by modification with a formylphenol compound, or the like. it can.

Of the above methods (i) to (v),
The method (i) of melt extrusion coating followed by modification with a formylphenol compound is advantageous and desirable in terms of ease of production and production cost. In providing an ethylene-vinyl alcohol-based copolymer coating layer modified with a formylphenolic compound on fibers and yarns, the coating layer is provided on a single fiber or a single yarn, and then a plurality of them are collected to obtain a desired layer. It is also possible to manufacture a yarn having a thickness equal to the required thickness or a yarn having a thickness close to the required thickness, and then cover the whole with the coating layer.

An example of the melt extrusion coating method, which is a desirable method for producing the coated fiber or the coated yarn of the present invention, will be specifically described below with reference to FIGS. First, FIG. 1 is an overall view showing a manufacturing process of a coated yarn coated with an ethylene-vinyl alcohol-based copolymer. 2 and 3 correspond to FIG.
FIG. 4 is a diagram showing a structure of a die provided in connection with the extruder 1 shown in FIG. 4, and FIG. 4 is a cross-sectional view of the coated yarn produced thereby cut at right angles in the length direction.

The ethylene-vinyl alcohol copolymer is melted by a screw type extruder 1 and guided to a die 2 connected to the extruder 1. As the die 2, a tube die shown in FIG. 2 or a pressurized die shown in FIG. 3 is used. A core thread 4 previously manufactured through a core bar 3 of a die 2
Is continuously supplied, and the periphery thereof is continuously coated with an ethylene-vinyl alcohol-based copolymer to produce a coated yarn 6 covered with an ethylene-vinyl alcohol-based copolymer layer 5. The coating yarn 6 is cooled and solidified in the cooling area 7 shown in FIG. 1, and is wound by a winding device 9 through a suitable means such as a nip roll 8 as necessary. The wound coated yarn 6 is denatured with a formylphenol compound in an appropriate processing apparatus (not shown) to acetalize the alcoholic hydroxyl group, and is denatured around the core yarn 4 shown in FIG. 4 with the formylphenol compound. The yarn of the present invention coated with the coated ethylene-vinyl alcohol copolymer layer 5 is produced.

In the above-mentioned melt extrusion coating method, the melt extrusion temperature of the ethylene-vinyl alcohol copolymer needs to be lower by at least 15 ° C. than the melting point or decomposition temperature of the core yarn. If the temperature difference is less than 15 ° C., the core yarn may be melted, thermally decomposed, etc., causing frequent breakage, making it difficult to perform normal melt extrusion coating.

It is desirable that the melt extrusion coating is performed using a tube type die shown in FIG. 2, in which case the ethylene-vinyl alcohol copolymer for coating is positively pushed into the core yarn. Due to the absence of voids, voids can be formed between the core yarn and the coating copolymer. In addition, since there is no fear of the copolymer flowing back into the core hole through which the core yarn runs, the core hole diameter can be increased. Therefore, machining of the cored metal hole becomes easy, the adaptability to the thickness and shape of the cored yarn is excellent, the running property of the cored yarn is good, and the threading can be easily performed by air sucker or the like. The workability is improved in that it is easy to pass even if there is a knot, and has various advantages.

On the other hand, when the pressing die shown in FIG. 3 is used in order to enhance the adhesiveness between the coating resin and the core yarn, conventionally, the core yarn having a flexible and inconsistent cross-sectional shape is used. Poor runnability and workability when supplying to the core, for example, excessive tension is applied to the core yarn due to excessive friction between the core metal hole and the core yarn, and the core metal hole or the molten copolymer heated to a high temperature may be damaged. Extra deformation and friction occurred in the contacted and softened core yarn, which often caused breakage of the core yarn. However, in the present invention, by controlling various requirements such as the running condition of the core yarn and the draft rate as described below, even in the case of using the press-type die shown in FIG. As in the case, the coated yarn coated with the ethylene-vinyl alcohol copolymer can be produced smoothly.

That is, in both the case of the tube type die shown in FIG. 2 and the case of the pressurized type die shown in FIG.
It is desirable that the core yarn be run from drawing to winding without substantially stretching. In addition, it was found that the circumferential length ratio, which is the ratio of the inner circumferential length of the coating resin to the outer circumferential length of the core yarn, was determined by the draft rate defined by the following equation and the amount of air brought in by the core yarn and the like. Draft ratio = A ÷ B In the above formula, A = cross-sectional area of the coated ethylene-vinyl alcohol-based copolymer portion when extruded from the die B = cross-sectional area of the ethylene-vinyl alcohol-based copolymer coating layer of the coated yarn

The draft rate is determined by the discharge amount of the copolymer from the die and the running speed of the core yarn. When the draft rate is large, the coated copolymer layer surrounding the core yarn is thinned and the draft ratio is reduced. Are reduced. On the other hand, when the amount of air brought in by the core yarn increases due to factors such as an increase in the traveling speed of the core yarn, the gap between the core yarn and the coating layer increases. In addition to the draft rate and the running speed of the core yarn, the control of pressurization or decompression of the air in the core metal is an effective means for setting the circumference ratio.

Then, the coated yarn coated with the drafted ethylene-vinyl alcohol copolymer is cooled and solidified as shown in FIG. 1, and then wound up. It is desirable to flatten the coated yarn by applying a pressure that causes plastic deformation by a nip roll 8 as shown in FIG. 3 or other suitable pressing means. It is possible to improve the property and increase the winding density. The nip roll and other pressing means used for flattening can be formed of a suitable material such as metal or rubber. The flatness (the value obtained by dividing the width of the cut cross section perpendicular to the length direction with the covering yarn by the thickness) is desirably 1.2 or more. However, excessive flattening causes cracking of the covering yarn, etc. A flatness of 1.2 to 4.0 is preferred. In addition, the wound coated yarn may be used as necessary to improve the degree of adhesion between the core yarn and the copolymer coating layer, to smooth the copolymer coating layer, and to make the cross-section circular if necessary. Heat treatment may be performed.

The fibers and yarns coated with the ethylene-vinyl alcohol copolymer modified with the formylphenolic compound of the present invention can be directly used directly for the production of products used in water such as fish nets and fish nets. can do. In addition, if necessary, blend with other fibers or yarns, blend,
By twisting, fiber products such as yarn, rope, string, net, knitted fabric, and nonwoven fabric can be further manufactured. Fibers of the present invention,
Yarn and textile products are fishery textile products such as fixed nets for fisheries used in long-term contact with seawater or freshwater, moss nets used for farmed fish and shellfish, and filtration filters for seawater and freshwater;
Rope used for mooring light buoys, buoys, etc .; can be effectively used as a pollution control fiber membrane used for civil engineering. Therefore, the present invention includes not only the above-mentioned fibers and yarns, but also fiber products produced therefrom.

[0037]

【Example】

Examples 1 to 3 Using methanol as a polymerization solvent, using azobis-4-methyloxy-2,4-dimethylvaleronitrile as a polymerization initiator, radical polymerization of ethylene and vinyl acetate under pressure at 60 ° C. , Ethylene content is 44 mol%
Of ethylene-vinyl acetate random copolymer (number average degree of polymerization: about 350). Next, the ethylene-vinyl acetate copolymer is saponified in a methanol solution containing caustic soda to produce an ethylene-vinyl alcohol copolymer in which 99 mol% or more of the vinyl acetate units in the copolymer are saponified. did.

After separating the water from the copolymer by a dehydrator, vacuum drying is carried out at a temperature of 100 ° C. or less, and the resultant is sufficiently dried.
An ethylene-vinyl alcohol copolymer for coating was obtained (8
Intrinsic viscosity [η] measured in a 5% aqueous phenol solvent at 30 ° C = 1.05 dl / g).

In the core hole of the screw type extruder equipped with the tube type die shown in FIG. 2, the number of twists of 10 times / m made of a polyester multifilament of 1000d / 192f was applied.
At a speed of 20 m / min., And passing the ethylene-vinyl alcohol copolymer obtained above at a die temperature of 22.
At 0 ° C., 150 per 100 parts by weight of polyester
After being melt-extruded and coated at a rate of 20 parts by weight, the coated yarn was cooled with room temperature air while being taken off at a speed of 20 m / min, solidified, wound up, and coated with an ethylene-vinyl alcohol copolymer (flatness: 1.8).

The ethylene-vinyl alcohol copolymer-coated yarn obtained above was immersed in a sulfuric acid solution containing 10 g / l of 4-formylphenol and sulfuric acid having a concentration shown in Table 1 at a bath ratio of 50: 1. At 90 ° C for 2 hours,
A formylphenol-modified ethylene-vinyl alcohol copolymer-coated yarn having a 4-formylphenol modification ratio (mol%) shown in Table 1 was produced.

Each coated yarn is twisted into a rope shape having a diameter of 6.7 mm, and each twisted yarn is left at a depth of about 1 to 2 m in the Seto Inland Sea for 18 months from April to October of the following year. Then, the state of adhesion of marine organisms was examined, and the results shown in Table 1 were obtained.

Comparative Example 1 A resin composition was prepared by blending 10% by weight of 2- (4-thiazolyl) -benzimidazole with the same ethylene-vinyl alcohol copolymer as used in Example 1. Extrusion coating was carried out in the same manner as in Example 1 except that the material was used for coating to produce a resin-coated yarn. A rope-like twisted yarn was produced from this resin-coated yarn in the same manner as in Example 1, and the state of adhesion of marine organisms was examined at the same time as in Example 1. The results shown in Table 1 were obtained.

Comparative Example 2 The same ethylene-vinyl alcohol copolymer used in Example 1 was added to 3- (3,4-dichlorophenyl) -1,1
-A resin composition was prepared by blending 10% by weight of dimethylurea, and melt-extrusion coating was carried out in the same manner as in Example 1 except that this resin composition was used for coating to produce a resin-coated yarn. . A rope-like twisted yarn was produced from this resin-coated yarn in the same manner as in Example 1, and the state of adhesion of marine organisms was examined at the same time as in Example 1. The results shown in Table 1 were obtained.

The state of attachment of marine organisms in Table 1 was visually determined according to the following criteria. 5 ··· No attachment of organisms is observed 4 ··· Living organisms adhere to about 20% of the surface area of the twisted yarn 3 ··· Organisms adhere to about 40% of the surface area of the twisted yarn 2 ... About 80% of the surface area of the twisted yarn is covered with attached organisms 1 ... The entire surface area (100%) of the twisted yarn is covered with attached organisms

[0045]

[Table 1]

From the results in Table 1, it is found that the twisted yarn of the present invention comprising the coated yarn coated with the ethylene-vinyl alcohol copolymer modified with formylphenol has no marine organism adhered even after 18 months. In the case of a coated yarn coated with a resin blended with a conventional marine biofouling inhibitor consisting of a urea compound or thiazolylbenzimidazole, while it can be used effectively in seawater for a long time or less. It can be seen that after 6 months, the entire surface of the yarn is covered with organisms and cannot be used effectively in seawater for a long time.

Examples 4 to 6 In the same manner as in Example 1, coated yarns coated with an ethylene-vinyl alcohol copolymer were produced. This coated yarn,
Using 3-formylphenol as a formylphenol-based compound, the mixture was treated in a sulfuric acid solution containing sulfuric acid having the concentration shown in Table 2 at a bath ratio of 50: 1 at 90 ° C. for 2 hours. A 3-formylphenol-modified ethylene-vinyl alcohol copolymer-coated yarn having a formylphenol modification ratio (mol%) was produced. A rope-like twisted yarn was produced from this coated yarn in the same manner as in Example 1, and the state of attachment of marine organisms was examined at the same time as in Example 1.
The results shown in Table 2 were obtained.

Examples 7 to 9 In the same manner as in Example 1, coated yarns coated with an ethylene-vinyl alcohol copolymer were produced. This coated yarn,
In a sulfuric acid solution containing 15 g / l of 3,5-dimethyl-4-formylphenol as a formylphenol compound and sulfuric acid having a concentration shown in Table 2, at a bath ratio of 50: 1 at 90 ° C. for 2 hours. By the treatment, a formylphenol-modified ethylene-vinyl alcohol copolymer-coated yarn having a 3,5-dimethyl-4-formylphenol modification ratio (mol%) shown in Table 2 was produced. From this coated yarn, a rope-like twisted yarn was produced in the same manner as in Example 1, and the state of adhesion of marine organisms was examined at the same time as in Example 1. The results shown in Table 2 were obtained.

[0049]

[Table 2]

From the results shown in Table 2, the case of the twisted yarn of the present invention comprising a coated yarn coated with an ethylene-vinyl alcohol copolymer modified with 3-formylphenol or 3,5-dimethyl-4-formylphenol Shows that no or little marine organisms adhere after 18 months, indicating that it can be effectively used in seawater for a long period of time.

[0051]

Industrial Applicability The fibers, yarns and fiber products of the present invention have high safety to fish and shellfish and human body, are durable without elution or falling off from the fiber products, and can adhere aquatic organisms for a long time. Can be prevented. In addition, the fibers, yarns and fiber products of the present invention have smooth and non-rough surfaces and are not flexible and hard, so that they do not cause damage to captured or cultured fish and shells, and furthermore, twist, warp and weave. It has good workability in knitting, knitting, rope making, and the like, and has extremely good workability in actual use.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of an overall process for producing a coated yarn of the present invention.

FIG. 2 is a view showing one example of a tube type die used for producing the coated yarn of the present invention.

FIG. 3 is a view showing an example of a pressure die used for producing the coated yarn of the present invention.

FIG. 4 is a diagram showing a cross section of an example of the coated yarn of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Extruder 2 Die 3 Core metal 4 Core thread 5 Ethylene-vinyl alcohol copolymer layer 6 Coated thread 7 Cooling area 8 Nip roll 9 Winding device

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI D02G 3/36 D02G 3/36 3/44 3/44 D06M 15/333 D06M 15/333 (58) Fields surveyed (Int.Cl. . ^6, DB name) D06M 13/00 - 15/715 C08F 16 / 38,116 / 38,216 / 38 A01N 61/00

Claims (5)

(57) [Claims] 1. Fibers and yarns coated with an ethylene-vinyl alcohol copolymer modified with a formylphenol compound. 2. The following Chemical Formula 1, Chemical Formula 2 and Chemical Formula 3; Embedded image Embedded image Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group or a phenyl group. The fiber or yarn according to claim 1, which is coated with an ethylene-vinyl alcohol copolymer modified with two or more kinds. 3. A textile product produced from the fibers or yarns of claim 1. 4. The fiber or yarn according to claim 1, which is used in contact with seawater or freshwater. 5. The textile product according to claim 3, which is used in contact with seawater or freshwater.