JPS6245712A - Conjugate monofilament having high knot strength - Google Patents

Abstract

PURPOSE:To obtain the titled monofilament, having an island component of a thermoplastic polymer having small flexibility in a specific state scattered in a sea component of a thermoplastic polymer having greater flexibility and suitable for fishery and industrial use. CONSTITUTION:Conjugate monofilaments having island components (B-1), (B-2)...of a thermoplastic polymer having small flexibility scattered in dots from the central part of the cross section to positions near the outer periphery thereof in a sea component (A) of a thermoplastic polymer having greater flexibility. All the island components (B-2)-(B-7) at an equal distance from the central part of the cross section are of the same size, and the shortest distance (l) from the outer periphery to the island components is within 3-15%, particularly 3-10% range based on the filament diameter.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a composite monofilament having excellent knot strength and particularly suitable for fishing and industrial use.

(Prior Art) The logical explanation of the expression of monofilament nodule strength +q has not yet been elucidated, and various improvement plans have been proposed based on experience and hypotheses.

In terms of improving the quality of monofilaments, the first requirement is to improve physical strength.

However, it is a well-known fact among those skilled in the art that although tensile strength does improve by stretching under severe conditions, knot strength peaks at a certain point and begins to decline as the stretching conditions are strengthened. Therefore, it is common knowledge in industry that operating conditions are set with a balance between tensile strength and nodule strength.

Therefore, a major challenge in monofilament spinning technology is how to approach tensile strength by increasing knot strength while maintaining high tensile strength.

Typical methods conventionally proposed for this purpose include (1) a method of copolymerizing the primary polymer to increase orientation while suppressing the generation of microcrystals that contribute little to strength; (2) A method of optimizing the conditions for spinning, cooling, and stretching; and (3) A method of stretching the monofilament 1- and then reducing the orientation of the surface layer thereof. It is true that each of these methods has been used to improve the nodule strength based on estimation and hypothesis, and it is true that the nodule strength improvement effect has been recognized to some extent, but the effectiveness is still insufficient. It's hard to say.

(Problems to be Solved by the Present Invention) Therefore, the inventors of the present invention conducted extensive research with the aim of obtaining a monofilament with superior knot strength.
Especially in monofilaments with composite i-structures,
To achieve this purpose, we need to understand that the difference in circumference between the inner and outer circumferences due to the curvature of the thread that occurs when tying knots, and how to make the thread itself less susceptible to damage due to tightening. The inventors discovered that the unique composite structure of monofilament having a3 in cross section is compact and achieved the present invention.

(Means for Solving the Problems) In other words, the present invention provides a composite monofilament in which two types of thermoplastic polymers having different flexibility are joined together, the thermoplastic polymer having high flexibility being (A) [hereinafter referred to as polymer Δ
In the h component, an island component consisting of a thermoplastic polymer (B) with low flexibility [hereinafter referred to as polymer B] is present from the center of the cross-section of the monofilament to a position close to the outer periphery. The present invention provides a high knot strength composite monofilament characterized in that a plurality of island components are scattered at equal distances from the center of the cross section and are essentially equally spaced and of equal fit size.

Polymer A and polymer B used in the present invention include nylon 6, nylon 66, nylon 6'IO, nylon 1
1. Polyamides such as nylon 12 and nylon 612, polyethylene phthalate 1~, polyesters such as polybutylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene and polypropylene, and vinylidene halides such as polyvinylidene fluoride and polyvinylidene chloride. Examples include polymers and copolymers thereof. These polymers contain plasticizers, antioxidants, heat stabilizers, weathering agents, lubricants, antistatic agents,
Conventional additives such as dye 11 and face 1 can be included in desired amounts.

There are no particular restrictions on the combination of Polymer A and Polymer B other than the fact that they have different flexibility, but in order to further improve the physical performance of the resulting monofilament, two types of polymers with excellent mutual adhesion may be used. It is desirable to select a combination. Furthermore, it is more desirable to select a combination of polymers that have similar spinnability under the same spinning conditions and exhibit a common stretching effect under the same stretching conditions.

For example, if you choose nylon 6 as polymer B,
As the polymer A, it is preferable to select a copolymer of nylon 6 and nylon 66, etc., and as the polymer A, it is preferable to select a polyethylene or the like which has poor adhesion to nylon 6 and has a different drawn strip fl. do not have.

Regarding the difference in flexibility between Polymer A and Polymer B, we investigated various combinations of polymers, and found that various factors such as differences in adhesion and spinnability between the combined polymers, and the degree of handling are delicately intertwined. Although it has been difficult to establish numerical regulations such as the extent to which differences in characteristics should be present, it is common sense to recognize that combinations of flexible materials are effective. However, common sense suggests that the combination U of polymers with flexibility may be exemplified by the following combinations.

■Polymer A: Polymer Δ with 10% N-butylbenzenesulfonamide added as a plasticizer during spinning Polymer B: Sulfuric acid Nylon 6 with relative viscosity of 3.7 ■Polymer A
: Nylon 6/66 copolymer with a sulfuric acid relative viscosity of 3.7 and a composition weight ratio of 90/10 Polymer B: Nylon 6 with a sulfuric acid relative viscosity of 3.8 Polymer A
Polymer B: Melt index (JIS K6760
) 0.350/min high-density polyethylene In the present invention, in order to combine these two types of polymers with different flexibility and develop high knot strength, it is necessary to regulate the composite form as follows. be.

As shown in the drawing (enlarged cross-sectional view showing one embodiment of the composite monofilament i~ of the present invention), a sea component A consisting of polymer A having high flexibility is composed of polymer B having low flexibility. A plurality of seven island components B-1 to B-7 are scattered from the center of the cross-section of the monofilament to a position close to the outer periphery.Here, the large serrations of the seven island components are shown evenly in the drawing. is an island component B equidistant from the center of the cross section.
−2 to 7 are essentially equally spaced and ′;
The size of the q suspension is important. Therefore, the island component [3-1 in the drawing can be drawn larger or smaller than the other;+:, components [3-2 to 7, and roughly (
Of course, it is also possible to make the δ component B-1 have a different size from the island components [13-2 to 13-7, and to have a plurality of them scattered.

Here, the shape of the island component does not necessarily have to be a wrinkled circular cross section, but from the viewpoint of ease of manufacturing the nozzle and the effect of achieving high nodule strength, it is pointless to purposely make the island component have an irregular cross section. It is also advantageous to set it on an industrial setting. However, even if the set circular cross section may be distorted or deformed to some extent due to the difference in melt viscosity between the island component (polymer B) and the sea component (polymer A), composite position, composite weight ratio, etc., the purpose of the present invention There is no problem in achieving this goal.

Next, important requirements regarding the cross-sectional shape of the composite monofilament of the present invention will be explained.

First, the less flexible polymer B was continuous within the monofilament cross section, like the core layer or sheath layer of a triple core-sheath structure, or the middle layer of a triple core-sheath structure. If the structure is used as an interrogation, the desired effect will not be achieved. Comparing the case of the core layer or sheath layer of Zunarichi triple core-sheath structure, the intermediate layer of triple core-sheath structure, and the case of scattering them in an island shape according to the present invention, the latter has a higher weight of polymer B. Since the outer circumference with respect to the foot, in other words, the contact with the polymer A is long, the adhesion between the two is good, and the knot strength is reduced by 1.

Second, the sheath layer and bonding of the double core-sheath! In the type composite yarn, it is necessary that the polymer B is not exposed on the surface of the cross section of the monofilament, but is scattered in the form of islands in the sea component consisting of the polymer A. If Polymer B is exposed on the surface of the monofilament cross section, no matter how good the adhesive properties of Polymer Δ and B are, unless they are exactly the same, they will always fail under the harsh conditions of use A1. While the peeling cause 1 phenomenon occurs and the composite yarn loses its meaning, by scattering polymer B in the form of islands inside the sea component as in the present invention, the above peeling concave 1 phenomenon is improved. This maintains high knot strength and durability.

Thirdly, it is necessary that the polymers [3, which are scattered in the form of islands, are scattered from the center of the cross section of the monofilament to a position as close to the outer periphery as possible. However, if it gets too close to the outer periphery and the layer of polymer Δ that covers it becomes too thin, this is not preferable because it will cause problems with the strength of the outer periphery of Porin A. This strip '1 depends on the diameter of the monofilament white and the adhesiveness of polymers A and B, but the shortest distance from the outer periphery of the monofilament cross section to the island component (Q in the drawing) is 3 to 15% of the monofilament diameter. , especially in the range of 3 to 10%. If this α is less than 3% of the monofilament diameter, the strength at the outer periphery of the polymer A covering the polymer B will become a problem, and if it exceeds 15%, it will not be possible to develop high knot strength, which is not preferable.

In addition, island components made of polymer B are formed (it is desirable that they exist in large numbers and have a small diameter, but
241. Problems with the machining quality of the nozzle, and problems with the silk reeling technology. ',: The diameter is 0.07 to 3.
．． In the 0# monofilament, it is appropriate that the number of island components is 7 or more, especially 13 or more, and the diameter of the island component is in the range of 3 to 50%, especially 5 to 30% of the monofilament diameter.

If the number of island components is less than 7, it is not preferable because the meaning of scattering the island components is lost and high nodule strength cannot be achieved. Also, the diameter of the island component is 3% of the monofilament diameter.
If the diameter is less than 50%, there will be restrictions in manufacturing the die, especially for monofilaments with a small diameter. This is not preferable because it becomes less meaningful and has the opposite effect on the development of nodule strength.

Furthermore, distributing the island components equidistant from the center point of the monofilament's cross-section at essentially equal intervals and in equal amounts means that the resulting monofilament is not curvatured by the knots at any location in the cross-section. It is an indispensable factor for achieving the same effect and not causing curling due to component imbalance, and even if one of the above requirements is lacking, the desired high knot strength can be obtained. I can't.

The composite monofilament of the present invention is produced by composite spinning two types of polymers in a conventional manner using a composite spinneret designed to satisfy the above-mentioned cross-sectional shape. After bonding the seed polymers together,
It can be manufactured by cooling, then stretching and heat setting as necessary.

The composite monofilament of the present invention, which is thus 1q, is
It has high knot strength and is particularly suitable for fisheries and rice industries.

(Action of the invention) Although the reason for the high knot strength in the composite monofilament of the present invention is not clear, the polymer B with low flexibility is scattered from the center of the cross section of the monofilament to near the outer periphery, and This is due to the fact that the presence of highly flexible polymer A in some places alleviates the strain inside the thread that occurs when the monofilament knots, and as polymer A deforms, damage to polymer B is reduced. It is assumed that.

Furthermore, in general, the tensile strength and knot strength of monofilament tend to be higher as the wire diameter becomes smaller, and this is due to distortion inside the yarn due to the fact that the surface layer and center portion are not cooled at the same time. It is estimated that However, the reason why the composite monofilament of the present invention can achieve high knot strength even with a relatively thick wire diameter is because the island components, which are supposed to mainly contribute to strength, are scattered in small shapes, so that the outer and inner peripheries of each island component are scattered. It is presumed that this is because the cooling of the parts is not strictly simultaneous, but is carried out in a relatively short period of time, resulting in highly uniform cooling. This is similar to a state in which a large number of thin monofilaments, which tend to exhibit high strength, are converged.

The present invention will be described in more detail with reference to Examples below.

In addition, in the examples (the tensile strength, J, and the knot strength are
This is a value measured according to the regulations of JIS L-1013.

In addition, the bending hardness can be measured by shaking the object (monofilament) perpendicularly to stainless steel bales with a diameter of 2# placed parallel to each other with an interval of 8#, and hooking the material in the center. Measure the maximum stress (g) when handling between two stainless steel bars with a rod, and calculate the cross section vfi (1MI2
). The handling speed for moving the hook was 50 mm/min, and the atmospheric condition 1'1 at the time of measurement was set to 20'C165%RH. The monofilament to be measured was left in advance in an atmosphere of 20'C, 165% RH for 2/1 hour or more before being subjected to measurement.

(Example) Nylon 6/nylon 66 copolymer (composition ratio 90/
10) as a sea component (polymer Δ) and nylon 6 having a relative viscosity of 3.8 as an Ω component (polymer B), seabird-type composite nofilamen 1 to 1 were produced by a composite spinning method.

That is, the temperature of the spinning machine was set at 285°C, and after extruding the polymer from the spinning nozzle, the undrawn monofilament L~ was cooled and solidified in a cooling water bath with a water surface at a distance of 7 cm from the nozzle and a bath temperature of 7°C. , followed by 5. in a heat medium bath heated to 210'C. /95°C after stretching to 1x
5% relaxation in a hot water bath! While heat-treated, the diameter is 0.
．． A drawn monofilament of 285 Nn was wound up at a speed of 160 m/min.

In the above method, the number (n) of island components, their position (from the outer periphery of L-section to the island component The shortest distance to the monofilament diameter (expressed as a ratio % to the monofilament diameter) and its size (P = average diameter of the island component expressed as a ratio % to the monofilament diameter x number of Ω) are different. A monofilament was obtained.

In addition, individual monofilaments made of polymers A and B were spun using the same thread 1 as described above to obtain comparative 1 non-pull.

The physical property evaluation results of each monofilament obtained are shown in the table.
1 shows all the details.

As is clear from the results in Table 1, composite monofilaments (No. 2.3.4.6 and No. 9
) has high knot strength and excellent tensile strength.

On the other hand, the number nG of island components needs to be 7 or more, and those that do not satisfy this thread A41 (No. 1) do not improve knot strength, and a difference is observed from the single thread of polymer B (Nα12). do not have.

Furthermore, even if the number of seats n2l-3J and the island size P are the same, if the shortest distance from the cross-sectional periphery of the monofilament to the island component is smaller than 3% of the monofilament diameter (Nα5), at nodulation The sea component near the outer periphery is destroyed by bending, and only low knot strength is exhibited at the rake.
exceeds 15% of the monofilament diameter (No,
7> On the contrary, the nodule strength decreases.

Furthermore, the size P of the island component is 3 of the monofilament diameter.
It is necessary to be ~50%, and if it is less than 3% (NQ10), and if it exceeds 50% (No, 8).
high nodule strength cannot be obtained.

For JPNα3, J, and 9, the size of the island component located at the center of the monofilament cross section is larger than other island components,
Although this is an example in which P is close to the limit of 50%, the knot strength of the monofilament in this case shows a slightly lower value than in other examples.

For reference, a single monofilament 1 was spun from Polymer A and Polymer B under the same conditions as above to obtain a diameter of 0.
As a result of wrapping 285# drawn yarn and measuring the bending hardness, which is a measure of the flexibility of the monofilament, it was found that Polymer A
Monofilament 1- (J: 92 g/2,
The monofilament made of Polymer B showed a value of 115 g/M'', and Polymer Δ was about 20% softer than Polymer BJ:.

(Effect of the invention) As explained above, the composite monofilament of the present invention]-
J5 exhibits unprecedented high knot strength in the single fiber diameter range of 0.07 to 3.0 m, and is expected to be applied to various uses such as J5 J for fishing and industrial use.

[Brief explanation of drawings]

The drawing is an enlarged cross-sectional view showing one embodiment of the high knot strength composite monofilament of the present invention. A... Sea component (polymer △) B... Island component (polymer B) Patent applicant Azuma Monofilamen I ~ Co., Ltd. Figure!

Claims (2)

[Claims] (1) A composite monofilament in which two types of thermoplastic polymers with different flexibility are joined, in which a thermoplastic polymer (A) with a high flexibility contains a thermoplastic polymer with a low flexibility. A plurality of island components made of the plastic polymer (B) are scattered from the center of the cross-section of the monofilament to a position close to the outer periphery, and the island components located at equal distances from the center of the cross-section are essentially equally spaced and equally spaced. A high knot strength composite monofilament characterized by a large quantity. (2) The distance from the cross-sectional outer periphery of the monofilament to the island component and the diameter of the island component account for 3 to 15% and 3 to 50% of the monofilament diameter, respectively, and the number of islands is 7 or more. A high knot strength composite monofilament according to claim (1).