JP2002069742A - High-specific gravity yarn - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber having a combination of high sinkability with sufficiently high mechanical strength with no problem in view of fishnet manufacturing processing and having such high durability and weatherability as to cause no mechanical strength drop even if used for a long period in the form of a fishnet. SOLUTION: This fiber in the form of a high-specific gravity yarn is characterized by including 1,000-200,000 ppm of at least one kind of inorganic microparticles 0.01-5.0 μm in average size and >=2.5 in Mohs'hardness in a melt-spinnable fiber and having a specific gravity of >=1.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber having a high specific gravity and a high strength and suitable for use in industrial materials. The present invention relates to a fishing net which has no problem of marine environmental pollution and has excellent durability, especially excellent wear resistance. It relates to suitable fibers.

[0002]

2. Description of the Related Art Conventionally, as a fishery material represented by fishing nets, fishing ropes, etc., it has been superior to natural fiber products in terms of water resistance, corrosion resistance, strength, abrasion resistance and durability. Synthetic resin fiber products exhibiting properties have been used. However, the water content is lower than that of natural fiber products, and the specific gravity is relatively small, so the sedimentation in seawater and the shape retention against tidal currents are unsatisfactory, and there is a problem that its use is subject to many restrictions. I was

[0003] Various proposals have been made to overcome such problems, but the most noticeable technology is to increase the specific gravity of the fibers and ropes themselves to increase their sedimentation in water. As a means for increasing the specific gravity of fibers and ropes themselves, there is a technique of kneading metallic lead or a compound thereof into fibers.However, when a metallic lead compound or the like is used, it is used as a guide in the fiber manufacturing process and processing process. There is a possibility that the material may fall off from the fiber due to the friction or elute into seawater while being used as a fishing net, causing a problem of lead pollution. Further, when the used fishing net is discarded, there is a possibility that a similar pollution problem may occur such that harmful components including lead remain after discarding, and there has been a problem that it cannot be easily disposed of. On the other hand, as a means not using a lead compound, for example, vinylidene chloride-based fibers having a relatively large specific gravity have been used. However, with the development of the net-making technology, high-strength fibers that can be stably provided for high-speed net-making. As a result, vinylidene chloride fiber has a problem of insufficient strength. In addition, fishing nets made of vinylidene chloride fiber also have a problem that it is difficult to incinerate them because hydrogen chloride gas is generated during incineration. As described above, not only high specific gravity but also high strength, pollution-free properties, wear resistance, and the like have been required.

Various proposals have been made for such a demand. Specific examples include (1) a fiber obtained by uniformly dispersing a high specific gravity powder such as zinc or lead in a synthetic filament (for example, Japanese Patent Publication No. 51-37378, Japanese Patent Application Laid-Open No. 56-61936, JP-A-61-613), (2) A high specific gravity powder is mixed and dispersed in a low softening point resin,
Fibers obtained by further mixing this mixture with a resin for imparting strength (for example, Japanese Patent Publication No. 57-20407);
(3) Cored fibers having a mixture of a low softening point resin and a high specific gravity powder as a core layer and a strength-imparting resin as a sheath layer (for example, JP-A-58-4819).

However, even the above proposals are not sufficient, and no solution has been found such as a method for achieving a balance between conflicting performances such as high specific gravity and abrasion resistance, and a method for imparting abrasion resistance.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide both high sedimentation and sufficient fiber strength which does not cause a problem in net processing, and excellent durability which does not decrease in strength even when used as a net for a long period of time. An object of the present invention is to provide a fiber having water resistance and weather resistance.

[0007]

That is, the present invention is as follows. 1. The average particle size in the melt spun fiber is from 0.01 to 5.
1 of inorganic fine particles having a Mohs hardness of 2.5 or more at 0 μm
A high specific gravity yarn containing 1,000 to 200,000 ppm of a seed or more and having a specific gravity of 1.5 or more. 2. The inorganic fine particles have an average particle size of 0.01 to 1.0 μm.
m, inorganic fine particles (A) having a Mohs hardness of 2.5 or more and inorganic fine particles (B) having an average particle size of 0.1 to 5.0 μm and a Mohs hardness of 2.5 to 5 Said 1
The high specific gravity yarn described. 3. A composite fiber having a core-in-sheath structure, containing 10 to 200,000 ppm of high specific gravity inorganic fine particles in the core component, and 10 or more inorganic fine particles having a Mohs hardness of 2.5 or more in the sheath component.
A high specific gravity yarn containing from 00 to 200,000 ppm and having a specific gravity of 1.5 or more. 4. The volume ratio of the core component in the composite fiber is 20
% Or higher specific gravity.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The high specific gravity yarn of the present invention has a specific gravity of 1.5 or more, and is excellent in abrasion resistance because inorganic fine particles having a Mohs hardness of 2.5 or more are present on the fiber surface.

The high specific gravity yarn of the present invention has a specific gravity of 1.5 or more. If the specific gravity is less than 1.5, the specific gravity of a fishing net or a fishing net rope is insufficient, and the sedimentability in water is poor. Preferably, 1.
7 or more, more preferably 1.9 or more.

The inorganic fine particles used in the present invention must have an average particle size of 0.01 to 5.0 μm. If the particle size is too large, clogging, poor drawing, yarn breakage, fluff, and the like may be caused during the spinning and drawing steps. On the other hand, if the particle size is too small, wear resistance cannot be obtained. The particle size distribution is preferably sharp without containing particles of 10 μm or more in order to lower the friction coefficient of the fiber surface and to prevent the occurrence of dropout. Particularly preferably, the volume content of the particles having a size of 2 μm or more is 5% or less.

The average particle diameter of the inorganic fine particles described above is
The diameter at the integrated 50% point of the equivalent sphere particle size distribution calculated based on the Stokes equation is shown.

The inorganic fine particles having a Mohs hardness of 2.5 or more in the present invention include titanium dioxide (TiO ₂ ), iron oxide (Fe
₂ O ₃ , Fe ₃ O ₄ ), silicon dioxide (silica, SiO ₂ ), silicon carbide (Si
C), alumina (Al ₂ O ₃ ), calcium carbonate (CaCO ₃ ), barium sulfate (BaSO ₄ ), calcium fluoride (CaF ₂ ), and the like. Among these, it is more preferable to contain one or more of them from the viewpoints of slipperiness and wear resistance.

If the Mohs hardness is less than 2.5, the improvement in wear resistance required for the present invention cannot be obtained.

It is necessary that the total content of the inorganic fine particles contained in the fiber is 1,000 to 200,000 ppm. If it is less than 1000 ppm, the desired wear resistance cannot be obtained, which is not preferable. In addition, when it is more than 200000 ppm, in the spinning and drawing step, due to high hardness, spinning,
At the same time, the machine base tends to be damaged during stretching, weaving and the like, and at the same time, clogging, stretching failure, and yarn breakage are not preferred. More preferably, 5000 to 70000 ppm
It is.

Even if only one kind of the inorganic fine particles is added to the fiber, good abrasion resistance is exhibited. However, when only one kind of inorganic fine particles having a large particle diameter is added, the possibility of dropout increases. It is preferable to add two or more kinds of inorganic fine particles having different particle diameters, because they have an effect of preventing dropout of large particles.

That is, if there is only one kind of large particle,
The force applied to the fiber surface is borne by only one type of particle, and when a large force is applied to the interface between the particle and the fiber, dropout tends to occur. However, by adding two or more types of particles having different particle diameters, the force acting on the interface between the particles and the fibers can be small, and the force acting on the fiber surface can be carried by the large particles, causing dropout. Without
Abrasion resistance can be improved.

As the inorganic fine particles having different particle diameters, inorganic fine particles (A) having an average particle diameter of 0.01 to 1.0 μm and a Mohs hardness of 2.5 or more are contained in the fibers of 1000 to 19900.
0 ppm, average particle size 0.1-5.0 μm, Mohs hardness 2.5
Of inorganic fine particles (B) having a size of
1000 ppm, content of (A) + (B) is 20
It is preferably at most 0000 ppm. In particular, it is more preferable that the inert inorganic fine particles (A) and (B) to be added are alumina, silica, and calcium carbonate, respectively.

As the alumina fine particles, gibbsite,
Bayerai, crystalline alumina hydrates such as Nordstrandite, boehmite, diaspore, todite, amorphous gels, boehmite gels, amorphous alumina hydrates such as Bayerite gels, and furthermore, ρ, η, γ, χ, κ, δ,
Intermediate activated aluminas such as theta-type and α-type aluminas are included, and among them, the δ-type and the γ-type are particularly preferable.

Although the silica fine particles may be used in any form, spherical silica fine particles are particularly preferred from the viewpoint of the effect of improving the abrasion resistance.

The calcium carbonate fine particles are calcite classified into trigonal system or hexagonal system, aragonite classified into orthorhombic system, vaterite classified into hexagonal system or pseudo-hexagonal system according to their crystal structures. In the present invention, any type of crystal can be effectively used, and the shape thereof is also a chain particle, a cubic crystal, a spindle shape, a columnar shape, a needle shape, and a spherical shape. It is possible to use an arbitrary shape such as an egg shape.

The method for adding the above-mentioned inert inorganic fine particles is not particularly limited. For example, when a polyester resin is used, a method of adding it in an esterification step, a transesterification step, a polycondensation step in producing a polyester, A method of blending the obtained polyester chips when drying, a method of directly adding them at the time of spinning, a method of melting a master chip containing a high concentration of inorganic fine particles and blending with a separately melted base polyester before spinning (melt blending method) ), A known method such as a method of blending a master chip and a base chip containing a high concentration of inorganic fine particles (a chip blending method) can be adopted. In consideration of productivity and the like, the most preferable is to create a master chip in advance and A method of spinning ester blended. Inorganic fine particles can be added to the polyamide system by adding it during a possible process.

The above-mentioned polyester resin and polyamide resin used in the present invention can be colored by adding a coloring agent, if necessary, so that the dyeing step can be omitted, which is preferable. The dye and / or pigment to be used can be realized by adding a dye and / or pigment during melt spinning, which is generally performed. Examples of the colored pigment include carbon black and phthalocyanine, and examples of the fluorescent white dye used for increasing white color include benzoxazole-based compounds, but are not limited thereto. Existing dyes and pigments can be used as long as they do not adversely affect the operability at the time of melt-spinning, or the strength, discoloration, deterioration, etc. necessary for use as a fiber or textile product. The preferred amount of the dye and / or pigment added is 0.
It is in the range of 3 to 1.0% by mass. The method for adding the colorant is also obtained by the method described as the method for adding the inorganic fine particles, for example, an esterification step, a transesterification step, and a polycondensation step in the production of polyester, and a polycondensation method. Method of blending dried polyester chips when drying, method of directly adding during spinning, method of melting master chips containing a high concentration of a coloring agent and blending them with a separately melted base polyester before spinning (melt blending method) Any known method such as a method of blending a master chip and a base chip containing a coloring agent at a high concentration (a chip blending method) can be adopted, but the quality stability, operation stability, and production Considering the properties, the most preferable is to create a master chip in advance and blend it with the base polyester It is a method of yarn.

The resin used in the present invention is not particularly limited as long as it is a resin that can be melt-spun, but it is preferable that the specific gravity of the resin itself is large. In addition, because the strength of the fiber is also required,
As the resin that can be melt-spun, a polyester resin and a polyamide resin are preferable.

The high specific gravity yarn of the present invention may be a composite fiber having a core-sheath structure. In this case, a high specific gravity inorganic fine particle of 1000 to 200,000 ppm is used as the core component, and an inorganic fine particle having a Mohs hardness of 2.5 or more is used as the sheath component.
２００200000 ppm or less. By adopting such a configuration, it is possible to achieve both properties such as strength, specific gravity, and abrasion resistance of the fiber. If the amount of the inorganic fine particles contained in the core component is less than 1000 ppm, a desired specific gravity cannot be obtained. On the other hand, if it is more than 200,000 ppm, the spinning drawability decreases, which is not preferable. Similarly, if the sheath component is less than 1000 ppm, the abrasion resistance is not excellent.
If it is more than 00 ppm, the spinning drawability will be poor. When the Mohs hardness is less than 2.5, the wear resistance is poor.

The ratio of the core component in the composite fiber is preferably at least 20% by volume. 20 core components
If it is less than 10%, the fiber strength is insufficient and is not practical. It is preferably at least 30%. The volume ratio of the core component is preferably 95% or less. If it exceeds 95%, the effect of the sheath component tends to hardly be exhibited.

In the fiber of the present invention, inorganic fine particles having a higher specific gravity can be added as long as the degree of surface protrusion of the added particles is not impaired and the spinning and stretching properties are not impaired.
In particular, in the case of a fiber having a core-in-sheath structure, by adding inorganic fine particles having a high specific gravity to the core component and adding Mohs hardness to the sheath portion, and adding inorganic fine particles having a prescribed particle size, more excellent wear resistance is obtained. High specific gravity yarn can be obtained. Specific examples of the inorganic particles having a high specific gravity include aluminum oxide, zinc oxide, tungsten, ferric oxide, titanium oxide, barium sulfate, triiron tetroxide, and cupric oxide.

The fiber of the present invention has a tenacity of 3.2 g / dte.
It is preferably at least x. In the case of less than 3.2 g / dtex, if the fiber alone is used as a fishing net or a rope, the net is easily broken or cut, which is not preferable. It is preferably at least 3.5 g / dtex, more preferably 3.6 g / dtex.
tex or more.

The high specific gravity yarn of the present invention can be obtained by a usual production method as described below. For example, when a polyester-based high specific gravity yarn is obtained, a polyester base chip and a polyester master chip containing one or more kinds of inorganic fine particles are weighed and mixed in a predetermined amount, and the mixed chip is supplied to an extruder and melted. It is a polyester polymer and subsequently spun from a spinneret.

The spun yarn is cooled and solidified by cold air after passing through a heating tube and a heat retaining tube. Further, after applying the oil agent, the take-up speed is 300 to 2000.
It is picked up by a roller whose peripheral speed is controlled to m / min.

The drawn undrawn yarn may be subjected to drawing as it is, or after the undrawn yarn is wound up,
It may be stretched. The undrawn yarn is 70 to 180 ° C.
Is stretched 1.5 to 6.0 times between two pairs of rollers and a heating zone, the heating of which is controlled in the range described above, and the obtained drawn yarn is wound into a package.

The obtained drawn yarns are put together in a unit of several or several tens, twisted or tied, and used as a rope. Further, a sheet-like material may be formed by knitting or weaving structure and used as a net. Since the yarn of the present invention is particularly a high specific gravity yarn, it is suitable as a rope net for fishery applications.

[0032]

The present invention will be described in more detail with reference to the following examples. The physical properties and evaluations in the examples were obtained as follows.

(1) Average particle size: The point of 50% integration in the equivalent spherical distribution obtained by a centrifugal sedimentation type particle size distribution analyzer (SA-CP-2 or CP-3) manufactured by Shimadzu Corporation is the average particle size. And

(2) Raw yarn strength / elongation: Measured at a sample length of 100 mm and a tensile speed of 100 mm / min using a Tensilon tensile tester manufactured by Orientec.

(3) Retention rate of wear resistance: JIS-L109
5 Using the tester shown in 7.10.2B, 300
After the reciprocating rubbing motion 0 times, the strength was measured by the method shown in (2). The abrasion resistance retention represents the strength of the yarn after the rubbing treatment with respect to the strength of the yarn without the rubbing treatment. It is preferable that the abrasion resistance retention is 85% or more.

(4) Specific gravity: The apparent density was measured using a specific gravity bottle.

(5) Degree of surface protrusion of the added particles: After washing the single yarn of the raw yarn with carbon tetrachloride,
The surface of the raw yarn was observed at a magnification of 10,000 times, and the number of protrusions present in a certain visual field was counted.

Example 1 4% by mass of a master chip resin containing 20% by mass of calcium carbonate having an average particle size of 0.56 μm in a polyethylene terephthalate-based chip
Then, spinning was performed. The yarn discharged from the spinneret was cooled and solidified by blowing cooling air to apply an oil agent, and then taken out at a spinning speed of 500 m / min. The drawn yarn was drawn in a drawing step. The obtained drawn yarn was approximately 5.5 dtex / filament.

Table 1 shows the specific gravity, high elongation, and abrasion resistance retention of the drawn yarn obtained above. As is clear from the results in Table 1, the polyester yarn of Example 1 secured the specific gravity required as a high specific gravity yarn, and the strength and elongation required as ropes and nets. At the same time, the smoothness of the surface was increased by the inorganic fine particles, and an improvement in the retention of wear resistance was realized.

Example 2 A master chip resin containing 20% by mass of calcium carbonate having an average particle size of 0.56 μm and a master chip resin containing 20% by mass of silica having an average particle size of 0.08 μm in a polyethylene terephthalate-based chip Was mixed so as to be 4% by mass, and then spinning was performed. Otherwise, Example 1 was followed.

Table 1 shows the specific gravity, high elongation and wear resistance retention of the drawn yarn obtained above. As is clear from the results in Table 1, the polyester yarn of Example 2 secured the required specific gravity as a high specific gravity yarn, and the required strength and elongation as ropes and nets. At the same time, the surface smoothness was increased by the inorganic fine particles, and an improvement in the retention of wear resistance was realized.

Comparative Example 1 Spinning was performed in the same manner as in Example 1 except that spinning was performed without adding inorganic fine particles.

Table 1 shows the specific gravity, high elongation, and abrasion resistance retention of the drawn yarn obtained above. As is clear from the results in Table 1, the polyester yarn of Comparative Example 1 did not have a high specific gravity and had poor abrasion resistance.

Comparative Example 2 As inorganic fine particles, a master chip resin containing 20% by mass of calcium carbonate having an average particle size of 0.56 μm was mixed at 2.5% by mass and then spun. Otherwise, Example 1 was followed.

The specific gravity, high elongation, and abrasion resistance retention of the drawn yarn obtained above are shown in Table 1. As a result, yarn breakage occurred frequently, resulting in poor spinnability, and it was difficult to obtain a yarn.
Thus, Comparative Example 2 was not a preferable condition.

Example 3 Spinning and stretching were carried out in the same manner as in Example 1 except that a nylon 66 polymer chip was used. The results obtained are shown in Table 1. From this result, the yarn of Example 3 required specific gravity as a high specific gravity yarn, and a rope,
The necessary strength and elongation as a net were secured. At the same time, the surface smoothness was increased by the inorganic fine particles, and the retention of wear resistance was improved.

[0047]

[Table 1]

Example 4 As a core component, a master chip resin containing a polyethylene terephthalate-based chip containing 2% by mass of triiron tetroxide fine particles having an average particle size of 1.0 μm was adjusted to 4% by mass with respect to the core component. After mixing, spinning was performed. The same resin as in Example 1 was used for the sheath component. The core / sheath components were merged in the nozzle, and the core / sheath volume ratio of the yarn obtained from the die was adjusted to 70/30. Then, cooling air was blown to cool and solidify to give an oil agent. Thereafter, it was taken out at a spinning speed of 330 m / min. The drawn yarn was drawn in a drawing step. The obtained drawn yarn was approximately 5.5 dtex / filament.

The results obtained are shown in Table 2. From these results, the yarn of Example 3 secured the specific gravity required as a high specific gravity yarn, and the strength and elongation required as a rope and a net.
At the same time, the surface smoothness was increased by the inorganic fine particles, and the retention of wear resistance was improved.

Example 5 In Example 4, a master chip resin containing 20% by mass of barium sulfate having an average particle diameter of 1.2 μm in the core component was mixed so as to be 4% by mass with respect to the core component. And except that the core / sheath ratio was 80/20,
A yarn was produced in the same manner as in Example 4.

As shown in Table 2, the fibers of Example 5 had the specific gravity required for high specific gravity yarn, and the strength and elongation required for ropes and nets.
At the same time, the surface smoothness was increased by the inorganic fine particles, and the retention of wear resistance was improved.

Example 6 A yarn was produced in the same manner as in Example 4 except that the core / sheath volume ratio was changed to 20/80.

As shown in Table 2, the fibers obtained in Example 6 secured the specific gravity required for a high specific gravity yarn, and the strength and elongation required for ropes and nets. At the same time, the surface smoothness was increased by the inorganic fine particles, and the retention of wear resistance was improved, but the operability was slightly poor.

[0054]

[Table 2]

[0055]

According to the present invention, a yarn excellent in spinning and drawability and having both high specific gravity and abrasion resistance can be obtained. The high specific gravity yarn of the present invention can satisfy the sedimentation property and high strength required for industrial material applications, particularly fishing nets, marine ropes, and the like,
In particular, since it has excellent wear resistance, it is possible to provide ropes and nets which can be used for a long period of time and are excellent as materials for marine products without fear of marine pollution.

Claims (4)

[Claims] 1. The melt spun fiber has an average particle size of 0.1.
A high specific gravity yarn containing at least one kind of inorganic fine particles having a Mohs hardness of 2.5 or more and a specific gravity of not less than 1.5 and a specific gravity of 1.5 or more. 2. The method according to claim 1, wherein the inorganic fine particles have an average particle size of 0.01 to 0.01.
1.0 μm, inorganic fine particles (A) having Mohs hardness of 2.5 or more, average particle size of 0.1 to 5.0 μm, Mohs hardness of 2.5
2. The high specific gravity yarn according to claim 1, comprising inorganic fine particles (B) having a particle size of from 5 to 5. 3. A conjugate fiber having a core-sheath structure, wherein high specific gravity inorganic fine particles are contained in a core component at 1000 to 200,000 ppm.
A high specific gravity yarn, comprising 1000 to 200,000 ppm of inorganic fine particles having a Mohs hardness of 2.5 or more in a sheath component and having a specific gravity of 1.5 or more. 4. The high specific gravity yarn according to claim 3, wherein a volume ratio of the core component in the conjugate fiber is 20% or more.