JP2788336B2 - Fishing net - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial application field> The present invention relates to a fishing net with improved abrasion resistance and flex fatigue resistance, and more particularly to a fishing net by treating it with a specific treating agent. The present invention relates to a fishing net with improved flex fatigue resistance.

<Prior Art> As a material for fishing nets such as fixed nets and lathe nets, organic fibers such as polyester, nylon and vinylon are usually used. However, in recent fisheries-related industries, there is a need to reduce the weight of nets due to the aging of workers, to reduce the flow resistance of nets in the sea, and to increase the speed of fishing boats and transport efficiency. There is a strong demand among related companies for the utilization and deployment of organic fibers with high specific strength to fishing nets. To meet this demand, the industry has
Attempts have been made to utilize so-called organic high-strength fibers (fibers with high specific strength) such as aramid fibers and wholly aromatic polyester fibers. However, these organic high-strength fibers are generally resistant to tension in the fiber axis direction, but on the other hand, due to friction from the direction perpendicular to the fiber axis, that is, friction between the fiber and the object or friction between the fiber and the fiber. In addition, a part of the fiber surface is easily damaged by fibrillation. Therefore, the abrasion resistance is inferior, and for the same reason, there is a problem that the bending fatigue resistance is also inferior.This problem causes bending fatigue due to waves in seawater during operation, and gravel, Stone rocks,
This has become an important issue because it has become extremely difficult to deploy it in the fishing net field due to significant wear on parts of the hull.

Conventionally, as means for improving such abrasion resistance and bending fatigue resistance, net impregnation of a net with various resins, or nets using impregnated yarns have been widely used. , Rubber-based, urethane-based, polyolefin-based, vinyl acetate-based resins and the like are used. For example, as a technique using a polyurethane-based resin as an abrasion-resistance improving agent, "Abrasion-resistance improving agent" (JP-B-62) −53
No. 634) and “Abrasion-resistant fishing net” (Japanese Patent Publication No. 1-2588).

Certainly, it has been recognized that fishing nets surface-coated or impregnated with the treatment agents described in the above prior art have improved wear resistance and flex fatigue resistance. However, in the case of fishing nets, they are rubbed in seawater or in a state where seawater is interposed,
When abraded, with the above-mentioned treating agent, the treating agent film swells due to seawater, and the strength of the film decreases, and the adhesiveness of the fiber to the treating agent film also decreases. In addition, the fabric cannot exhibit its properties, and the treating agent falls off during the use of the net. As a result, the fibers are worn and damaged, so that they have a drawback that they cannot sufficiently exhibit the inherently excellent fiber performance.

<Object of the Invention> The present invention was devised as a result of earnest research to solve such disadvantages in the prior art, and its object is to improve abrasion resistance and bending fatigue resistance. In particular, it is to provide a fishing net made of organic high-strength fiber.

The present inventors have conducted various studies in order to achieve the above object, and as a result, a net treated with a treating agent obtained by blending polyurethane, polyethylene oxide, a fluororesin, and an ethylene urea compound in an appropriate ratio. Alternatively, the present inventors have found that a net knitted using a treated yarn has solved the above-mentioned drawbacks and has excellent abrasion resistance and bending fatigue resistance, and has reached the present invention.

<Constitution of the Invention> That is, the present invention provides (1) polyurethane (A), polyethylene oxide (B),
Fishing nets treated with an abrasion resistance improving agent containing a fluororesin (C) and an ethylene ethylene urea compound (D) as main components (2) The polyurethane (A) comprises a polycarbonate polyol and an aliphatic polyisocyanate, The molecular weight of the polyethylene oxide (B) is from 1,000 to 7000, and the fluororesin (C) is a tetrafluoroethylene polymer, a trifluoroethylene chloride polymer, a tetrafluoroethylene hexafluoropropylene copolymer, From the group consisting of tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene / perfluoroalkyl vinyl ether copolymer, vinylidene fluoride polymer, ethylene / tetrafluoroethylene copolymer Including one or more selected,
A compound wherein the ethylene urea compound (D) satisfies the following general formula: Wherein R is an aromatic or aliphatic hydrocarbon residue, and n is 0, 1 or 2. When n = 0, the terminal is a hydroxyl group. ] The fishing net according to claim 1, wherein

(3) The weight ratio of each component is (A) / [(A) + (B) + (C) + (D)] = 0.34-0.70 (B) / [(A) + (B) + (C) + (D)] = 0.24 to 0.60 (C) / [(A) + (B) + (C) + (D)] = 0.03 to 0.20 (D) / [(A) + (B) + (C) + (D)] = 0.03 to 0.15. The fishing net according to claim 1 or 2.

Here, polyurethane is a high molecular polymer obtained by a reaction between a polyether polyol and a polyisocyanate, and a reaction between a polycarbonate polyol and a polyisocyanate. A polymer obtained by the reaction is preferred. Examples of the polyisocyanate include aliphatic or aromatic polyisocyanates such as hexamethylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, and naphthylene diisocyanate. Aliphatic polyisocyanates are preferred from the viewpoint of properties.

The oxidized polyethylene is obtained by oxidizing polyethylene to have a low molecular weight, preferably having a hydroxyl group and / or a carboxyl terminal group, and more preferably an oxide of high density polyethylene having a molecular weight of 1,000 to 7000. .

 The ethylene urea compound is represented by the following general formula.

Wherein R is an aromatic or aliphatic hydrocarbon residue, and n is 0,
1 or 2. When n = 0, the terminal of R is a hydroxyl group. ] Typical compounds are octadecyl isocyanate,
Reaction products of aromatic or fatty acid isocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, and triphenylmethane triisocyanate with ethyleneimine. Used in the form of

Fluorinated resins include tetrafluoroethylene polymer, trifluoroethylene chloride polymer, tetrafluoroethylene hexafluoropropylene copolymer, tetrafluoroethylene perfluoroalkyl vinyl ether copolymer, Ethylene / propylene hexafluoride / perfluoroalkyl vinyl ether copolymer, vinylidene fluoride polymer, ethylene / tetrafluoroethylene copolymer and the like.

The fluororesin is usually used in the form of a dispersion obtained by dispersing a particulate fluororesin in a dispersion medium using a dispersant, or a water emulsion obtained by emulsifying the particulate fluororesin in an aqueous medium using an emulsifier. Is done.

Examples of the treatment method using the treatment agent of the present invention include a spray method,
Any conventionally known method such as a coating method may be used, but a liquid obtained by mixing each aqueous dispersion of polyurethane (A), polyethylene oxide (B), fluorine resin (C) and ethylene ethylene urea compound (D) is used. The simplest method is to immerse and impregnate the yarn fiber or the knitted fishing net, then dry and heat treat. Of course, it may be knitted into various fishing nets suitable for market use after applying the treatment agent in the form of a thread-like fiber according to the method described above,
After knitting into various fishing nets suitable for market use, the treating agent may be applied by the above-described method.

The weight ratio of each component in the treating agent is as follows: a) (A) / [(A) + (B) + (C) + (D)] = 0.34-0.70 b) (B) / [(A) + ( (B) + (C) + (D)] = 0.24 to 0.60 c) (C) / [(A) + (B) + (C) + (D)] = 0.03 to 0.20 d) (D) / [( A) + (B) + (C) + (D)] = 0.03 to 0.15. When the weight ratio of the above a) is less than 0.34, the strength of the treated agent film formed on the surface of the treated fiber or fishing net is not sufficient, and the interfacial adhesion between the film formed by the treating agent and the fiber is poor. This is not preferable because sufficient abrasion resistance and bending fatigue resistance required as a fishing net cannot be obtained. On the other hand, if it exceeds 0.70, the surface abrasion resistance of the coating increases and the smoothness and abrasion resistance become insufficient.

If the weight ratio of b) is less than 0.24, the surface friction resistance of the treated fiber or the treatment agent film formed on the surface of the fishing net is insufficiently reduced, and the desired smoothness and abrasion resistance cannot be obtained. If it exceeds 0.60, not only the strength of the coating formed by the treating agent will be insufficient, but also the interfacial adhesion between the coating formed by the treating agent and the fibers will decrease, and the durability will undesirably decrease.

When the weight ratio of c) is less than 0.03, the surface friction resistance of the treated fiber or the treatment agent film formed on the surface of the fishing net is not sufficiently reduced, and the water absorption and swelling of the film by seawater are prevented. Therefore, wear resistance and bending fatigue resistance in the presence of seawater cannot be sufficiently exhibited. On the other hand, if it exceeds 0.20, the strength of the film formed by the treatment agent becomes insufficient, and the interfacial adhesive strength between the film and the fiber also decreases, which is not preferable because sufficient properties cannot be exhibited.

Further, if the weight ratio of d) is less than 0.03, the strength of the film formed by the treatment agent is insufficient, and if it exceeds 0.15, the flexibility of the film formed by the treatment agent is insufficient, and the fiber or fishing net after treatment is insufficient. The bending fatigue resistance of the steel is lowered, and the intended purpose cannot be achieved.

Therefore, it is preferable to control the weight ratio of each active ingredient by blending the treating agent so as to be in the ranges described in the above a), b), c) and d). Fishing nets treated within this weight ratio range generally have significantly improved abrasion resistance and bending fatigue resistance, and have very little reduction in wear resistance and bending fatigue resistance when seawater is present. Good.

The solid concentration of the treating agent is suitably from 1 to 25% by weight, and preferably from 5 to 20% by weight. Drying temperature is 100-1
The drying time is preferably 0.5 to 20 minutes at 50 ° C and the drying temperature is 1 minute.
If the temperature is lower than 00 ° C., the formation of a film by the treating agent becomes insufficient,
On the other hand, when the temperature exceeds 150 ° C., evaporation of water in the treating agent occurs rapidly, so that a good film cannot be formed.

The heat treatment temperature is preferably from 160 to 240 ° C and the heat treatment time is preferably from 0.2 to 10 minutes. If the heat treatment temperature is lower than 160 ° C, the formed film is insufficiently crosslinked and cannot exhibit good film strength, and exceeds 240 ° C. And the coating deteriorates, and the strength decreases.

The amount of the treatment agent film attached to the fishing net after treatment (the solid content weight of the treatment agent) is appropriately 1 to 15% by weight,
Preferably it is 3 to 10% by weight. If the amount is less than 1% by weight, the improvement of wear resistance and bending fatigue resistance is insufficient, so that a practical effect as a fishing net is not exhibited. If the amount exceeds 15% by weight, the fishing net after treatment becomes extremely coarse and hard. Flexural fatigue is lowered, which is not preferable in practical use.

The reason why the fishing net treated with the treating agent of the present invention is excellent in abrasion resistance and bending fatigue resistance is that polyurethane having both light resistance and water resistance and good adhesion to fibers is added to polyethylene oxide having a low friction coefficient. And a fluororesin in combination to form a soft and smooth, water-absorbing and water-resistant coating on the fiber surface. This is because the cohesive force of the particles is improved. Therefore, the fishing net treated with this treating agent has a small coefficient of friction and has an effect of reducing the friction between the single fibers and the friction between the fibers / objects, thereby preventing the single fibers from being fibrillated. Abrasion resistance and bending fatigue resistance of fishing nets are improved, and durability is extended.

<Effects of the Invention> The present invention has the following effects.

(1) The abrasion resistance of a fishing net treated with the treating agent of the present invention in the air and in the presence of seawater is extremely excellent.

(2) The fishing net treated with the treating agent of the present invention has extremely excellent bending fatigue resistance in the air and under the presence of seawater.

<Examples> Twisted yarn cords and knotless nets made of para-aramid fibers that are liable to fibrillate by friction will be described below, and the effects of the treatment agent of the present invention will be specifically described with reference to examples. The evaluation of wear resistance and bending fatigue resistance was performed according to the following methods.

1) Abrasion resistance evaluation method A The evaluation apparatus is shown in FIG. In Fig. 1, 1 is 0.8m
A strained piano wire of mφ, 2 is a load, 3 is a twisted cord or a sample for evaluation of a cord-like form collected from a knotless fishing net.

In the figure, 0.2 g / d is applied to one end of the cord-like evaluation sample 3.
After the load of e is attached, the other end of the sample is reciprocated, and the number of reciprocations until the cord-shaped evaluation sample is cut by friction with the piano wire 1 is determined.

2) Abrasion resistance evaluation method B The evaluation apparatus is shown in FIG. In FIG. 2, 1 is a freely rotating roll having an outer diameter of 20 mmφ, 2 is a freely rotating roll having an outer diameter of 10 mmφ, 3 is a twisted cord, or a sample for evaluation of a cord-like form collected from a knotless fishing net, Reference numeral 4 denotes a pad for allowing seawater to intervene in the cord-shaped evaluation sample 3, and reference numeral 5 denotes seawater.

For the comparative evaluation, the cord-shaped evaluation sample 3 was twisted 1.5 times, and a roll 1 partially immersed in seawater 5 as shown in FIG.
And then apply 0.2g / de to one end of the cord-shaped evaluation sample 3.
Is applied, the other end of the sample is reciprocated, and the cord-like evaluation samples are compared with each other by the number of reciprocations until the cord-like evaluation samples are mutually worn and cut at the twisted place.

3) Flexural fatigue resistance evaluation method This is performed by the S-bending method using two pairs of freely rotating rolls having an outer diameter of 30 mmφ. After applying a twisted cord or a cord-shaped evaluation sample collected from a knotless fishing net to this roll in an S-shape, the tensile force is set to 2.5 g / denier, and the cord-shaped evaluation sample is reciprocated to cause bending fatigue. Then, a comparison is made based on the number of reciprocations until the cord-like evaluation sample is cut.

In order to search for and determine the optimum blending ratio of the treatment agent of the present invention, first, the yarn is treated in a fiber (yarn) form, and then the twisted cord having an average thickness similar to a general-purpose knotless fishing net using the treated yarn. Create a code for the wear resistance,
An example in which the bending fatigue resistance is comparatively evaluated will be specifically described.

Example 1 An aqueous dispersion of polyurethane (A) comprising a polycarbonate polyol and an aliphatic polyisocyanate (active ingredient 35% by weight), an aqueous dispersion of polyethylene oxide (B) having a molecular weight of 4500 (25% by weight of active ingredient) and 4 Aqueous dispersion of fluorinated ethylene polymer (C) (active ingredient 60% by weight) and aqueous dispersion of diphenylmethanediethylene urea (D) (active ingredient)
Each of the aqueous dispersions was blended so that the solid content ratio (wt%) shown in Table 1 was 25 wt%) to prepare a treatment liquid.
The solid concentration of the treatment liquid was 10% by weight.

A para-aramid fiber of 1500 denier / 1000 filament (technola, Teijin Ltd.) substantially free from an oil agent at the time of spinning is immersed in the treatment liquid to be impregnated, and dried at 120 ° C. for 2 minutes. Further, a heat treatment was performed at 180 ° C. for 1 minute to cause a crosslinking reaction of the treatment agent coating. At this time, the solid content of the treating agent was 5.0% by weight. The obtained treated aramid filaments are drawn and aligned in the Z direction 20 times / 1
After twisting with a twist number of 0 cm, this twisted yarn is further twisted, and 9
A 2,000 denier twisted cord was obtained. This twisted cord was evaluated for wear resistance A, B and bending fatigue resistance. The evaluation was as shown in Table 1.

Examples 2 to 10 are (A), (B),
Each of the aqueous dispersions (C) and (D) was mixed with the solid content ratio (% by weight of the active ingredient) of the corresponding examples shown in Table 1.
Ratio) to obtain the intended twisted cords, and the wear resistances A, B and the bending fatigue resistance were comparatively evaluated. . The results are as shown in Table 1.

Comparative Example 1 For comparison, the same aramid fiber as used in Example 1 was not impregnated with a treating agent, but was twisted in the same manner as in Example 1 to obtain a 9000 denier twisted cord. The results of evaluation in the same manner as in Example 1 are shown in Table 1 as Comparative Example 1.

Comparative Examples 2 to 13 Comparative Examples 2 to 13 were conducted in order to clarify the optimum range of the solid content ratio of the compounding agent in comparison with the examples, and were used in Examples 1 (A) and (B). ), (C) and (D) were prepared in the same manner as in Example 1 except that the treating agents were prepared by blending them so that the solid content ratio (% by weight of the active ingredient) was as shown in Table 1. The obtained twisted cord was evaluated.

Example 11 The same treatment agent as in Example 5 of Table 1 was used in the same manner as in Example 5 using a 1500 denier / 1000 filament aramid fiber provided with an oil agent in the spinning step. 1500 denier × 5 × 2/13 knotless knotless net, prototyped so that the number of twists using the treated yarn is about 1.6 turns / cm
A part of the trajectory between 00 and 00 was incorporated as a tear prevention net. After conducting an actual operation test for about four months, a part of the net was cut out, and a cord-like evaluation sample was taken from the cut net. The samples were evaluated for wear resistance A, B and flex fatigue resistance, and the results are shown in Table 2. The tensile strength of the sample was measured for reference, and the results are shown in Table 2.

Example 12 The same treatment as in Example 9 was carried out using the same treatment agent as in Example 9 using a 1500 denier / 1000 filament aramid fiber to which an oil agent was applied in the spinning step. A trial production was performed using the obtained treated yarn so that the number of twists was about 3.2 turns / cm.
The space between the 100 knots x 40 knotless nets of 1500 denier x 2/8 sections was incorporated into the body net of the trawl net. After conducting an actual operation test for about four months, a part of the net was cut out, and a cord-like evaluation sample was taken from the cut net. The samples were evaluated for wear resistance A, B and flex fatigue resistance, and the results are shown in Table 2. The tensile strength of the sample was measured for reference, and the results are shown in Table 2.

Comparative Example 14 The same aramid fiber as used in Example 11 for comparison was not impregnated with the treating agent, but a knotless network was prototyped in the same manner as in Example 11 to prevent a part of the trawl from tearing. After incorporating it into a net and conducting an actual operation test for about four months,
Evaluation was performed in the same manner as in Example 11. The results are shown in Table 2.

Comparative Example 15 For comparison, a knotless net was prototyped in the same manner as in Example 12, without impregnating the same aramid fiber as used in Example 12 with the treating agent. Approximately 4
After performing an actual operation test for five months, evaluation was performed in the same manner as in Example 12. The results are shown in Table 2.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a side sectional view showing a wear resistance evaluation device A. In the figure, 1 is a piano wire having a circular cross section of 0.8 mmφ, 2 load, 3
Is an evaluation sample. FIG. 2 is a side sectional view showing the wear resistance evaluation device B. In the figure, 1 is a freely rotating roll having an outer diameter of 20 mmφ, 2 is a freely rotating roll having an outer diameter of 10 mmφ, 3 is an evaluation sample, 4 is a pad, and 5 is water.

Claims (3)

(57) [Claims] 1. A fishing net treated with an abrasion resistance improving agent comprising polyurethane (A), polyethylene oxide (B), fluororesin (C) and ethylene urea compound (D) as main components. 2. The polyurethane (A) comprises a polycarbonate polyol and an aliphatic polyisocyanate, the polyethylene oxide (B) has a molecular weight of 1,000 to 7000, and the fluororesin (C) further comprises a tetrafluoroethylene polymer, Trifluorochlorinated ethylene polymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene / perfluoroalkyl vinyl ether copolymer A compound comprising at least one selected from the group consisting of a polymer, a vinylidene fluoride polymer and an ethylene / tetrafluoroethylene copolymer, wherein the ethylene urea compound (D) satisfies the following general formula: Wherein R is an aromatic or aliphatic hydrocarbon residue, and n is 0, 1 or 2. When n = 0, the terminal is a hydroxyl group. ] The fishing net according to claim 1, wherein 3. The weight ratio of each component is (A) / [(A) + (B) + (C) + (D)] = 0.34-0.70 (B) / [(A) + (B) + ( (C) + (D)] = 0.24 to 0.60 (C) / [(A) + (B) + (C) + (D)] = 0.03 to 0.20 (D) / [(A) + (B) + ( C) + (D)] = 0.03 to 0.15. The fishing net according to claim 1 or 2, wherein