JPH03137229A - As-spun yarn for fishing net and fishing net - Google Patents

Abstract

PURPOSE:To obtain the subject as-spun yarn having excellent resistance to decomposition with amine, high modulus and high specific gravity comprising a polyester core component mainly containing ethylene terephthalate and a polyamide sheath component, respectively having specific physical properties. CONSTITUTION:The objective as-spun yarn is composed of core-sheath type conjugate fiber comprising (A) core component of polyester containing ethylene terephthalate as principal ingredient and (B) sheath component of a polyamide. In said fiber, content of the component A is 30-90wt.%. Furthermore, said fiber has >=0.8 intrinsic viscosity [eta], 160X10<-3>-190X10<-3> birefringence and >=1.38g/cm<3> density of the component A and >=2.8 relative viscosity in sulfuric acid [etar], >=45X10<-3> birefringence and >=1.135g/cm<3> of the component B. Besides, polyhexamethylene adipamide is preferable as the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to raw yarn for fishing nets and fishing nets. More specifically, the present invention relates to a raw yarn for fishing nets that has excellent resistance to amine decomposition against ammonia and the like generated by corrosive decomposition of fish and shellfish, has a high modulus, and has a high specific gravity, and a fishing net using the raw yarn for fishing nets.

[Conventional technology]

Traditionally, raw yarn for fishing nets has mainly been made of polyamide or polyester fibers, with some polyethylene fibers also being used. Among them, polyester fiber has a high specific gravity,
Because it has the feature of high tensile strength underwater, it is particularly preferred in the fields of purse seine and fixed nets. Regarding improved polyester fibers used in fishing nets, Japanese Patent Publication No. 58-38530 and the like are disclosed.

[Problem to be solved by the invention]

Polyamide fibers used as yarn for fishing nets have excellent durability and resistance to amine decomposition, but have the disadvantage of low specific gravity and difficulty sinking.

Furthermore, because the modulus is low, there is also the drawback that the fishing net sways greatly due to waves, ocean currents, etc.

On the other hand, polyester fibers have a high modulus and a high specific gravity, which solves the problems of fishing nets using polyamide fibers, but the problem is that they have poor amine decomposition resistance and cannot withstand long-term use. was there. That is,
After fishing nets are used, they are dried on the beach, but during this process, the seafood still attached to the nets rots and generates ammonia, and when exposed to high temperatures due to sunlight, fishing nets made of polyester fibers are decomposed by amines. Therefore, fishing nets made of polyester fibers are strongly required to have improved resistance to amine decomposition.

As a method for solving the above-mentioned drawbacks of polyester fibers, the aforementioned Japanese Patent Publication No. 58-38530 describes that the single fiber denier and carboxyl group terminal concentration are specified, but in this case, the amine decomposition resistance is reduced to some extent. Although it is improved, the degree of improvement is extremely insufficient compared to the required level.

An object of the present invention is to solve the problems of the prior art described above, and to provide raw yarn for fishing nets that has excellent amine decomposition resistance, high modulus, and high specific gravity.

Another object of the present invention is to provide a fishing net that uses the fishing net yarn and has excellent amine decomposition resistance, high modulus, and high specific gravity.

[Means and effects for solving the problems] The present invention has the following features: (1) A yarn for fishing nets made of composite fibers, the composite fibers having a core component of polyester containing ethylene terephthalate as a main component; It is a core-sheath type composite fiber containing polyamide as a sheath component, and the ratio of the polyester core component is 30 to 30.
90% by weight, and the intrinsic viscosity [η] of the core component is 0.8.
Above, the birefringence is 160X10-" to 190X10-",
The density is 1.380 g/cm" or more, the sulfuric acid relative viscosity [ηr] of the polyamide sheath component is 2.8 or more, and the birefringence is 4.
5X10-3 or more and a density of 1.135 g/cm" or more, and (2) the fishing net yarn described in (1) above has a strength of 6. ．．
0g/d or more, elongation 20% or more, density 1.200g
/cm3 or more, initial tensile resistance is 60 g/d or more,
Dry heat shrinkage rate is 7% or more, wet knot strength is 5. (3) A fishing net characterized by using the raw yarn for fishing nets described in (1) above, (4) (2) ) is a fishing net characterized by using the yarn for fishing nets described in (a).

The contents and effects of each element constituting the present invention will be explained in detail below.

The yarn for fishing nets according to the present invention and the fishing net obtained using the yarn for fishing nets cannot be obtained with conventionally used polyamide fibers and polyester fibers, and have high modulus properties close to those of polyester fibers. It has amine decomposition resistance close to that of polyamide fiber, and the strength of raw yarn for fishing nets is 6.0 g/d or more, the elongation is 20% or more, and the density is 1.
．． 200g/cm3 or more, initial tensile resistance 60g
/d or more, and the wet knot strength is 5.0 g/d or more. The above-mentioned characteristics of the yarn for fishing nets according to the present invention are such that it is made of a core-sheath type composite fiber whose core is polyester and whose sheath is polyamide, and the polyester and polyamide fiber portions forming the core and sheath of the composite fiber are specified. It is characterized by having physical properties. That is, the intrinsic viscosity [η] of the polyester forming the core component is 0.8 or more, and the birefringence is 160.
X10-"~19-60XIO-", density 1. ．． 380 g/Cm" or more, and the relative viscosity of the sulfuric acid of the polyamide forming the sheath component [ηr
] is 2.8 or more, the -1 birefringence is 45 x 10-3 or more, the density is 1. ．． 135 g/cm" or less.

The polyester which is the core component of the composite fiber of the fishing net yarn of the present invention and the fishing net obtained using the fishing net yarn is preferably a polyester consisting essentially of polyethylene terephthalate units.

The copolymer component may be contained to an extent that does not substantially reduce the physical and chemical properties of the polyethylene terephthalate polymer, for example, less than 1.0%. The copolymerization components may include dicarboxylic acids such as isophthalic acid, naphthalene dicarboxylic acid, and diphenylcarboxylic acid, and diol components such as ethylene oxide, propylene glycol, and butylene glycol.

Strength of yarn for fishing net according to the present invention 6. In order to obtain a polyethylene terephthalate core component of the composite fiber of the raw yarn for fishing nets of the present invention, the intrinsic viscosity [η] is 0.7.
As mentioned above, it is necessary to have a high viscosity, preferably 0°8 or more.

On the other hand, the polyamide that becomes the sheath component is polycapramide, polyhexamethylene adipamide, polytetramethylene adipamide, polyhexamethylene adipamide, polyhexamethylene dodecamide, polyhexamethylene terephthalamide, polyhexamethylene Isophthalamide, etc., and copolymers and blend polymers of two or more of these may be used, but polyhexamethylene adipamide is particularly preferred.

Similar to the polyester core component, the polyamide sheath component polymer needs to have a high degree of polymerization in order to obtain high-strength raw yarn for fishing nets and fishing nets, and the relative viscosity of sulfuric acid is 2.8 or more, preferably 3.
It is 0 or more.

The ratio of the polyester core component of the composite fiber related to the raw yarn for fishing nets of the present invention and the fishing net obtained using the raw yarn for fishing nets is 3.
It is 0 to 90% by weight. When the polyester core component is less than 30% by weight, the yarn for fishing nets can effectively utilize the high modulus of the polyester component, and the density becomes low, making it difficult to obtain preferable yarns for fishing nets and fishing nets. Can not.

On the other hand, if the polyester core component accounts for 90% by weight or more, the amine decomposition resistance of the polyamide sheath component cannot be fully expressed, and the polyester core component will cause amine decomposition, making it difficult to use the preferred raw yarn for fishing nets and fishing nets. can't get it.

In the raw yarn for fishing nets of the present invention and the composite fibers for fishing nets obtained using the raw yarn for fishing nets, both the polyester core component and the polyamide sheath component are highly oriented and crystallized, and the birefringence of the polyester core component is 160X10-3~190
X10-". If it is less than 160X10-3, the strength of the composite fiber is 6.Og/d or more, and the initial tensile resistance is 60g.
/d or more, and on the other hand, 190XIO-
If it exceeds 3, the bending fatigue resistance in water may deteriorate.

On the other hand, the birefringence of the polyamide sheath component is 45×10 −3 or more. If the birefringence is less than 45×10'', it is difficult to obtain high strength and high modulus raw yarn for fishing nets and fishing nets, and it is also difficult to sufficiently exhibit amine decomposition resistance.

Furthermore, the density of the yarn for fishing nets of the present invention and the composite fibers for fishing nets obtained using the yarn for fishing nets is such that the density of the polyester core component is 1.380 g/am3 or more, and the density of the polyamide sheath component is 1.380 g/am3 or more.
．． It is 135 g/cm8 or more. If the density is not higher than the above-mentioned specific value, the density of the fishing net yarn according to the present invention and the fishing net obtained using the fishing net yarn is 1,200 g/cm.
It does not have a high specific gravity of 8 or more, it does not sufficiently improve the bending fatigue resistance in water, and it is difficult to sufficiently exhibit the amine decomposition resistance, thereby obtaining preferable raw yarn for fishing nets and fishing nets. I can't.

The raw yarn for fishing nets according to the present invention characterized by the above has a high strength of 6.0 g/d or more, an initial tensile resistance of 60 g/d or more, and an elongation of 20% or more, and is a preferable raw material for fishing nets. A fishing net using this yarn for fishing nets becomes a high-strength fishing net.

Preferred embodiments for producing fishing net yarn according to the present invention and fishing nets obtained using the fishing net yarn are as follows.

The raw yarn for fishing nets according to the present invention and the fishing net obtained using the raw yarn for fishing nets are composed of composite fibers consisting of a polyester core and a polyamide sheath. A polymer consisting essentially of polyethylene terephthalate and having a viscosity [η] of 0.75 or more, usually 0.85 or more is used.

On the other hand, as the polyamide sheath component polymer, a high polymerization degree polymer having a sulfuric acid relative viscosity of 2.8 or more, usually 3.0 or more is used.

It is preferable to use two extruder type spinning machines for melt spinning the polymer. The polyester and polyamide polymers melted by each extruder are introduced into a composite spinning pack, and spun into a composite fiber with polyester in the core and polyamide in the sheath through a composite spinning nozzle.

The spinning speed is 500 m/min or more. Immediately below the spinneret, a heated atmosphere of 200° C. or higher, preferably 260° C. or higher is created over a distance of 5 cm or more and within 1 m by providing a heat insulating cylinder or a heating cylinder. After passing through the above-mentioned heating atmosphere, the spun yarn is quenched and solidified with cold air, and then an oil agent is applied thereto and taken off by a take-up roll that controls the spinning speed.

Control of the heating atmosphere directly below the spinneret is important in order to maintain stringiness during spinning, and is particularly important at high speeds. The taken-off undrawn yarn is usually drawn continuously without being wound up, but it can also be drawn in a separate step after being wound up. The birefringence of the undrawn yarn sampled on the take-up roll in order to understand the physical properties of the undrawn yarn before stretching was 5X10-3 or more for the polyamide sheath and 10X1 for the polyester core.
It is oriented more than 0"".

If the spinning speed is less than 500 m/min, the durability of the core-sheath composite interface will be poor, making it impossible to obtain preferable raw yarn for fishing nets and fishing nets.

Next, the undrawn yarn is hot drawn at a temperature of 80°C or higher, preferably 120°C or higher. Stretching is performed in one stage or multiple stages of two or more stages, but the total stretching ratio is 1.5 to 6.5.
This is twice the range.

A fishing net is manufactured using the yarn for fishing net made of composite fiber manufactured by the method described above. Although the structure of the fishing net may be any generally known structure, it is preferable that the fishing net according to the present invention be manufactured and used as a fixed net or a purse net.

Examples will be explained below, and the definitions and measurement methods for the fiber structure parameters and fiber physical properties according to the present invention are as follows.

Characteristics of polyester fibers (a) Birefringence: After dissolving the polyamide sheath component in formic acid, sulfuric acid, fluorinated alcohol, etc., the fibers were measured by the interference fringe method using a transmission quantitative interference microscope manufactured by Carl Zeiss Jena (East Germany). The average birefringence observed from the side was determined. Measurements were taken at 2μ intervals from the surface layer of the fiber toward the center, and the average value was determined.

(b) Density: The polyamide sheath component is dissolved and removed with formic acid, sulfuric acid, fluorinated alcohol, etc., and carbon tetrachloride is removed with heavy liquid, n-
25 using a density gradient tube prepared with hebutane as a light liquid.
Measured at °C.

Characteristics of polyamide fibers (a) Birefringence: As with the polyester core fibers, only the polyamide fiber components in the surface layer were measured from the side using the interference fringe method using a transmission quantitative interference microscope.

(b) Density: The density of the composite fiber was measured at 25°C using a density gradient tube prepared using carbon tetrachloride as a heavy liquid and n-hebutane as a light liquid, and the density was determined from the density of the composite fiber and the density of the polyester core. Obtained by calculation.

3 14 [Example] Examples 1 and 2, Comparative Examples 1 to 3 Intrinsic viscosity [η) 1.05, carboxyl terminal group concentration 10
．． 5eq/106g of polyethylene terephthalate and polyhexamethylene adipamide (nylon 66, relative viscosity of sulfuric acid ηr3゜3) were each melted in a 40φ spinner, introduced into a composite spinning pack, and then spun into a core-sheath composite spinneret. It was spun as a composite yarn with a polyester part and a polyamide sheath part. The proportions of the core and sheath components were varied as shown in the table. The cap has a hole diameter of 0.8 mmφ and 5 holes.
0 hole was used. Polymer temperatures were as follows: polyethylene terephthalate was melted at 295°C, polyhexamethylene adipamide was melted at 29,000°C, and the spinning pack temperature was set at 300°C.
Spun as ℃. A 15 cm heating cylinder was attached directly below the mouthpiece, and the atmosphere inside the cylinder was heated to 290°C. The ambient temperature is the ambient temperature measured at a position 10 cm below the mouth surface and 1 cm away from the outermost thread.

A uniflow chimney with a length of 100 cm is installed under the heating cylinder, and cold air at 20°C is blown for 30 m from a direction perpendicular to the yarn.
It was sprayed at a speed of 1/min and cooled. The cooled and solidified yarn was oiled, the yarn speed was controlled by a take-up roll rotating at the speed shown in the table, and then the yarn was drawn continuously without being wound.

The film was stretched in three stages using five pairs of Nelson type rolls, then subjected to a relaxation heat treatment with 3% relaxation, and then wound up. The stretching conditions were as follows: take-up roll temperature at 60°C, first stretching roll temperature at 120°C, second stretching roll temperature at 150°C.
The third stretching roll temperature was 160°C, the tension adjustment roll after stretching was not heated, the first stage stretching ratio was 60% of the total stretching ratio,
The remainder was distributed and stretched in two stages. The spinning speed is 15
The yarn was spun at a speed of 00 m/min, and the fineness of the drawn yarn was approximately 500 denier. Two of the obtained drawn yarns were combined into 10
00 denier. In Comparative Example 1, the ratio of the core component to the sheath component does not satisfy the constituent requirements of the present invention.

Comparative Examples 2 and 3 are commercially available polyester fibers and nylon 6 fibers used for fishing nets.

The amine decomposition resistance of each fiber obtained in Example 1.2 and Comparative Examples 1 to 4 was evaluated at 135°C in ammonia gas.
The strength retention rate after 5 hours of treatment was evaluated, and the results are also listed in the table.

Next, each of the fibers obtained in Examples 1 and 2 and Comparative Examples 1 to 4 is twisted so that the twist coefficient becomes = 3000 at the time of pre-twisting, and then the two pre-twisted yarns are combined and the number of pre-twists x - twisted with a ply twist number of 0.6 to produce a net yarn with the same number of twists as the knotless net. This net yarn is dyed with disperse dyes (Miketon Polyester Red 2.0%, Miketon Polyester Yellow 0.8%, Miketon Polyester Blue 0.15%).
), Example 1.2 and Comparative Examples 1 and 3 were tested using moist heat 10
Dyeing under the conditions of 0°C x 30 minutes [7. Dry heat at 180° after air drying
Heat setting was carried out at CX 2 minutes x 1% stretching ratio relative to the length after dyeing. Comparative Example 2 was dyed under the conditions of moist heat at 130° C. for 30 minutes, air-dried, and then heat set at 200° C. for 2 minutes at a dry heat setting of 1% of the length after dyeing. The impact strength, stiffness, and durability of this net yarn were evaluated and are also listed in the table.

The impact test was performed using a high-speed tensile tester manufactured by Shimadzu Corporation at a test length of 25 cm and a tensile speed of 5 m/sec.

In addition, the mesh was attached to the chuck of the aforementioned tensile tester with an inner diameter of 10 mm.
A 3 cm metal ring was attached to the sample, and the resistance to pulling out the bow was shown when the ring was pulled out. The drawing speed was 30 cm/min, and a larger value indicates stiffness.

Durability was tested using an underwater fatigue tester manufactured by Shimadzu Corporation.
The figure shows the number of times the sample is cut at a rate of 1 time/second when the load is 14.4 kg and the operation is 0 kg.

(The following is a blank space) 7 8 -19- As is clear from the results in the table, the composite fiber that satisfies the constituent requirements of the present invention has extremely good amine decomposition resistance equivalent to that of nylon 6.

As is clear from the results in the table, the fiber for fishing nets made of composite fibers that satisfies the constituent requirements of the present invention has extremely good impact strength and stiffness equivalent to polyester fibers, and has extremely good impact strength and stiffness equivalent to nylon 6 fibers. Has good durability.

As is clear from the results in the table, the yarn for fishing nets made of composite fibers that satisfies the constituent requirements of the present invention has excellent amine decomposition resistance, high modulus, and high specific gravity. The resulting fishing net had good sedimentation properties, little swaying of the net in the sea, and excellent durability.

〔Effect of the invention〕

The yarn for fishing nets according to the present invention has a modulus equal to or higher than that of conventional polyester fibers, and has excellent amine decomposition resistance and durability equivalent to that of polyamide fibers. It also has excellent properties that could not be achieved with fishing net yarn made from polyamide fibers.

Furthermore, by using the fishing net yarn described above, the fishing net according to the present invention has characteristics such as high specific gravity, excellent sedimentation properties, and little swaying of the net in the sea, and has excellent amine decomposition resistance. There is. Therefore, it is possible to provide a fishing net that has excellent fishing performance and operability, and can withstand long-term use.

Claims (4)

[Claims] (1) Raw yarn for fishing nets made of composite fibers, the composite fibers being core-sheath type composite fibers having a core component of polyester containing ethylene terephthalate as a main component and a sheath component of polyamide; The ratio of ingredients is 30~
90% by weight, and the intrinsic viscosity [η] of the core component is 0.8.
Above, the birefringence is 160 x 10^-^3 ~ 190 x 10^
-^3, the density is 1.380 g/cm^3 or more, and the sulfuric acid relative viscosity [ηr] of the polyamide sheath component is 2.8 or more,
A fishing net yarn characterized by being made of a composite fiber having a birefringence of 45×10^-^3 or more and a density of 1.135 g/cm^3 or more. (2) The yarn for fishing nets according to claim (1) has a strength of 6.0 g/d or more, an elongation of 20% or more, an initial tensile resistance of 60 g/d or more, and a density of 1.200 g. /cm^
3 or more, dry heat shrinkage rate is 7% or more, wet knot strength is 5.0g
A raw yarn for fishing nets, characterized in that it has a yarn content of /d or more. (3) A fishing net characterized by using the yarn for fishing nets described in claim (1). (4) A fishing net characterized by using the fishing net yarn described in claim (2).