JP2000095937A - Polyamide resin composition for high strength monofilament and high strength monofilament - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition for a monofilament having a high strength and a monofilament having a high strength. SOLUTION: In a polyamide resin composition for high strength monofilaments containing polyamide resin compositions of different compositions, this polyamide resin composition contains from 78.0 to 85.0 wt.% ε-caprolactum residue (nylon 6 component), from 1.0 to 15.0 wt.% polyamide-forming residue (nylon 66 component) comprising adipic acid and hexamethylenediamine and from 3.0 to 22.5 wt.% ω-laurolactum residue (nylon 12 component), and the total of the three nylon monomer residues is 100 wt.%. A high strength monofilament comprises this polyamide resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyamide resin composition for a high-strength monofilament and a high-strength monofilament. More specifically, a polyamide resin composition capable of producing a high-strength monofilament, which could not be realized conventionally, by combining a polyamide resin having a specific composition in a specific range, and a polyamide resin composition The present invention relates to a high-strength monofilament made of a material.

[0002]

2. Description of the Related Art Polyamide monofilaments are used for fisheries applications such as fishing nets and fishing ropes, fishing lines,
Tennis net yarn, tennis racket gut, volleyball net yarn, sports ground windshield net yarn,
It is widely used in leisure related products such as rock climbing ropes for mountain climbing. Among these uses, monofilaments used in fisheries-related applications, especially as fishing lines for longline fishing, are mainly high-grade fish such as tuna, which are targeted for capture. Therefore, it is necessary to have high strength, but the conventional polyamide resin monofilament has a limit in strength.

[0003]

Conventionally, in order to compensate for the limitation in strength, a method of increasing the diameter of a monofilament has been used. However, increasing the diameter of the monofilament increases the amount of resin used, deteriorates roundness, increases the size of fishing boats, reduces storage space in narrow fishing boats, and reduces the amount of fishing gear that can be carried on fishing boats. There is a problem that the number of fishes decreases and that the fishes are conspicuous in the water, leading to a decrease in fishing results.

In view of such circumstances, the present inventors have made intensive studies to solve at once the disadvantages of insufficient strength of the conventional polyamide resin monofilament and the problems that accompany the insufficient strength. As a result of the superposition, a polyamide resin composition in which polyamide resins having different compositions are combined in a specific range, and the monomer residue of the polyamide resin constituting the resin composition is set to a specific ratio, thereby achieving a conventionally unattainable high resin composition. It has been found that a monofilament having high strength can be produced, and the present invention has been completed.

[0005]

Means for Solving the Problems In order to solve the above problems, in the first invention of the present invention, at least two components having different compositions are used.
In a polyamide resin composition for a high-strength monofilament containing a polyamide resin, the polyamide resin composition contains 78.0 to 85.0% by weight of ε-caprolactam monomer residue (6 nylon components), adipic acid and hexamethylene. 1.0-15.0% by weight of a polyamide-forming monomer residue (66 nylon component) composed of diamine;
And 3.0 to 22.5% by weight of an ω-laurolactam monomer residue (12 nylon component), and the total of the three types of polyamide resin-forming monomer residues is 100
The present invention provides a polyamide resin composition for high-strength monofilaments, characterized in that the amount of the polyamide resin composition becomes 0.1 wt%.

According to a second aspect of the present invention, in a high-strength monofilament produced from a polyamide resin composition containing at least two kinds of polyamide resins, the polyamide resin composition comprises an ε-caprolactam monomer residue (6
Nylon component) from 78.0 to 85.0% by weight, and a polyamide-forming monomer residue composed of adipic acid and hexamethylenediamine (66 nylon component) from 1.0 to 15.0.
% By weight and ω-laurolactam monomer residue (1
The present invention provides a high-strength monofilament characterized by containing 5.0 to 22.5% by weight of (2 nylon components) and having a total of 100% by weight of three types of polyamide resin-forming monomer residues.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polyamide resin composition for a high-strength monofilament according to the present invention contains 78.0 to 85.0 of ε-caprolactam monomer residues (meaning 6 nylon components or 6 nylon units derived from ε-caprolactam monomer).
% By weight. It is not preferable that the ε-caprolactam residue accounts for less than 78.0% by weight or more than 85.0% by weight of the entire polyamide resin composition, since the strength of the monofilament is not sufficiently exhibited. A particularly preferred range occupied by ε-caprolactam monomer residues is 78.0 to 80.0% by weight.

The polyamide resin that gives the ε-caprolactam monomer residue to the polyamide resin composition for a high-strength monofilament is not limited to one kind of polyamide resin, but may be derived from two or more kinds of polyamide resin components. The same applies to other monomer residues.

Examples of the polyamide resin component that provides an ε-caprolactam monomer residue include (a) a ε-caprolactam condensation polymer (6 nylon), and (b) a copolymerized polyamide comprising ε-caprolactam, hexamethylenediamine and adipic acid. 6/66 nylon), (c) a condensation polymer of ε-caprolactam and ω-laurolactam (6/12 nylon), (d) copolymerization of ε-caprolactam, hexamethylenediamine with adipic acid and ω-laurolactam There are four components of polyamide (6/66/12 nylon). Preferably, (b) 6/66 nylon or (c)
6/12 nylon or (b) 6/66 nylon
(c) Blends with 6/12 nylon. Among them, particularly preferred are (b) 6/66 nylon, (c) 6/12 nylon, or a blend thereof, which has a high ε-caprolactam residue content.

The polyamide resin composition for a high-strength monofilament according to the present invention comprises a polyamide-forming monomer residue consisting of adipic acid and hexamethylenediamine (a nylon component derived from two types of monomers,
(Meaning a nylon unit) must be contained in an amount of 1.0 to 15.0% by weight. If this monomer residue is less than 1.0% by weight, the strength of the obtained monofilament is not sufficient, and if it is more than 15.0% by weight, the continuous stretching stability is deteriorated, and the monofilament becomes too white to reduce the commercial value. It is undesirably low. A particularly desirable ratio of the 66 nylon monomer residue is 1.5 to 13.5.
% By weight.

The polyamide resin component for providing a 66-nylon monomer residue to the polyamide resin composition for a high-strength monofilament includes (e) a condensation polymer of hexamethylenediamine and adipic acid (66-nylon); ε
A copolymerized polyamide comprising caprolactam, hexamethylenediamine and adipic acid (6/66 nylon), (f) a copolymerized polyamide comprising ω-laurolactam, hexamethylenediamine and adipic acid (66 / nylon)
12 nylon), the above-mentioned (d) ε-caprolactam, copolymerized polyamide of hexamethylenediamine with adipic acid and ω-laurolactam (nylon 6/66/12),
And their blends. Among these, from the viewpoint of melting point and thermal stability,
(b) 6/66 nylon is particularly preferred.

The polyamide resin composition for a high-strength monofilament contains 5.0 to 22.5 ω-laurolactam monomer residues (meaning 12 nylon components or 12 nylon units derived from the ω-laurolactam monomer).
% By weight. If this residue is less than 5.0% by weight or more than 22.5% by weight, the strength of the monofilament is not sufficiently exhibited, which is not preferable. A particularly preferred range for the 12 nylon monomer residues is 7.0-20.0 parts by weight.

The polyamide resin component for providing a 12-nylon monomer residue to the polyamide resin composition for a high-strength monofilament includes the above-mentioned (c) a condensation polymer of ε-caprolactam and ω-laurolactam (6/12 nylon);
The above-mentioned copolymerized polyamide (66/66) comprising ω-laurolactam, hexamethylenediamine and adipic acid.
12 nylon), the above-mentioned (d) ε-caprolactam, copolymerized polyamide of hexamethylenediamine with adipic acid and ω-laurolactam (nylon 6/66/12),
And their blends. Among these, from the viewpoint of melting point and thermal stability, the above (c) 6
/ 12 nylon is particularly preferred.

In order to obtain a polyamide resin composition for a high-strength monofilament, at least two kinds of polyamide resins having different compositions are combined so that the residues derived from the above-mentioned various monomers for polyamide are in the above-mentioned range. Just do it. Among them, (b) a copolymerized polyamide (6/66 nylon) (polyamide B) composed of ε-caprolactam, hexamethylenediamine and adipic acid, and (c) ε-caprolactam and ω-laurolactam Is particularly preferred from the viewpoint of melt-blending properties in combination with a copolymerized polyamide (6/12 nylon) (polyamide C).

The monomer ratio of 6/66 nylon (polyamide B) is such that ε-caprolactam is 95 to 60% by weight,
Preferably, hexamethylene diamine and adipic acid are selected in the range of 5 to 40% by weight. If the monomer ratio is out of this range, fish eyes are likely to occur, which may cause stretching breakage during monofilament production, which is not preferable.
Particularly preferably, the former is 85 to 75% by weight and the latter is 15 to 75% by weight.
-25% by weight. The monomer ratio of 6/12 nylon (polyamide C) is such that ε-caprolactam is 95 to 75% by weight and ω-laurolactam is 5 to 25% by weight.
It is preferred to choose in the range of weight%. If the monomer ratio is out of this range, fish eyes are likely to occur, which may cause stretching breakage during monofilament production, which is not preferable. A particularly preferable range of the monomer ratio is as follows.
75% by weight, the latter being 10 to 25% by weight.

The blend ratio between polyamide B and polyamide C needs to be selected so that the above-mentioned three types of nylon monomer residues are within the above-mentioned range. The content of the three types of nylon monomer residues in the polyamide resin composition for high-strength monofilament is determined by the type, blend ratio, and content of the nylon monomer residue of the polyamide resin constituting the polyamide resin composition for high-strength monofilament. For example, it can be calculated for each polyamide resin composition.

If the melt viscosity of the polyamide resin used as a component of the polyamide resin composition for a high-strength monofilament according to the present invention is too small, a high-strength monofilament cannot be obtained. Using a temperature of 250 ° C., D = 1 mm, L / D =
10. It is preferable that the melt viscosity measured at a shear rate of 91 (1 / second) is selected within the range of 2000 to 30000 poise. Among them, preferred is a range of 3000 to 20000 poise, and particularly preferred is 4000 to 1800.
The range is 0 poise. When a blend is used, the difference in melt viscosity between the polyamide resins used is one.
It is preferably 0000 poise or less, and particularly preferably 7000 poise or less.

In the polyamide resin composition for a high-strength monofilament according to the present invention, in addition to the polyamide resin described above, various conventionally known resin additives are blended within a range that does not impair the strength of the high-strength monofilament. be able to. Examples of resin additives include hindered phenols, antioxidants such as phosphate esters and phosphite esters, ultraviolet absorbers such as benzotriazole compounds, light stabilizers, heat stabilizers, antistatic agents, lubricants, Plasticizers, dyes and pigments for coloring, rust preventives, water repellents and the like can be mentioned.

The high-strength monofilament according to the present invention comprises:
The polyamide resin composition for a high-strength monofilament can be produced as a raw material according to a conventional method. For example, first, melt and knead continuously with an extruder, continuously extrude from a spinning nozzle attached to the extruder tip, air,
The undrawn yarn is manufactured by immersing it in a cooling bath of water or ethylene glycol and cooling to produce an undrawn yarn, then biaxially drawing the undrawn yarn and performing a heat treatment. In the biaxial stretching, the first-stage stretching is performed 3- to 4.5-fold in steam or hot water at 95 to 120 ° C, and the second-stage stretching is performed in a range of 180 to
A method of stretching 1.1 to 2.5 times in a gas atmosphere at 300 ° C. is generally used. The monofilament thus obtained is obtained under a gas atmosphere at 160 to 350 ° C. under a temperature of 1.1 to 1.1 ° C.
Heat treatment is preferably performed at a winding ratio of 0.8 times.

The monofilament exhibits strength in proportion to the draw ratio, but the maximum draw ratio that can be stably drawn varies depending on the kind of resin constituting the raw material polyamide resin composition, and is therefore suitable for the raw material resin composition. It is desirable that the film be stretched at a stretch ratio that exhibits the highest strength. Regarding the melt-kneading temperature in the extruder, cooling conditions, stretching temperature, heat treatment conditions, and the like, it is preferable that stretching is performed by selecting a temperature suitable for each resin composition.

The high-strength monofilament according to the present invention comprises:
There is no particular limitation on the diameter, and the diameter can be changed depending on the application. Usually, the diameter can be selected in the range of 0.10 to 3.50 mm, and particularly preferably in the range of 1.80 to 2.9 mm. .

According to experiments by the present inventors, the monofilament has a tensile strength b of a filament made of polyamide B, a tensile strength c of a filament made of polyamide C, and a polyamide resin composition containing polyamide B and polyamide C. Assuming that the tensile strength of the product filament is a, it has been found that it is important that the ratio (strength ratio) of these a, b, and c satisfies the following formula (I). If the strength ratio represented by the formula (I) is less than 1.1, sufficient strength is not exhibited unless the diameter of the filament is increased, resulting in a large fishing gear.

[0023]

(Equation 2)

The high-strength monofilament according to the present invention comprises:
It can be widely used in fisheries-related applications such as fishing nets and fishing ropes, and leisure-related products such as fishing lines, tennis net yarns, tennis racket guts, and rock climbing ropes for mountain climbing. Among these applications, for fisheries-related applications, especially for fishing lines for longline fishing, the strength is high, so the diameter can be reduced, and the device is not large and the storage space in a narrow fishing boat is small. The amount of fishing gear that can be carried on a fishing boat is reduced, and the fishing line is not broken, and the fishing results are not reduced because it is not so noticeable in water.

[0025]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following description examples.

In the examples described below, the monofilament denier defines the weight of 9000 m as the monofilament denier.
A weight of 0 cm was measured, and a value obtained by multiplying the measured value by 10,000 was defined as a monofilament denier. The tensile strength of the monofilament was measured using Orientec Co., Ltd. Tensilon RTC-131-A type, with a chuck distance of 200 m.
The breaking stress (g) when the fiber was pulled under the conditions of m and a pulling speed of 200 mm was represented by a value (unit: g / denier) obtained by dividing by the diameter (denier) of the yarn.

In the examples described below, the polyamide resins used are those shown in Table 1 below. Novamid 2420A is 6/66 nylon manufactured by Mitsubishi Engineering-Plastics Corporation, the weight ratio of the copolymer components = 80/20 (% by weight), and the melt viscosity is 1000.
Nopomid 2020A is 6/66 nylon manufactured by Mitsubishi Engineering-Plastics Corporation, and the monomer component of the copolymer is 85/15 by weight.
(%), The melt viscosity is 10,000 poise, Novamid EN220 is 6/66 nylon manufactured by Mitsubishi Engineering-Plastics, and the monomer component of the copolymer is 75/25 (%) by weight. The melt viscosity is 9500 poise. Grillon CR8 is a 6/12 nylon manufactured by EMS Japan Co., Ltd. The monomer component of the copolymer is 78/22 (%) in weight ratio, the melt viscosity is 4300 poise, and the GLILLON CR9 is This is 6/12 nylon manufactured by the Company, and the monomer component of the copolymer is 90/10 (%) by weight and the melt viscosity is 5000 poise.

[0028]

[Table 1]

Example 1 Polyamide B listed in Table 1
-1 pellet and 50 parts by weight of C-1 pellet are blended and put into a hopper of an extruder, and continuously melted and kneaded at a cylinder temperature of 280 ° C., and a circular die having a diameter of 6.5 mmφ is used. And extruded into filaments. This filament is stretched 4 times in a steam atmosphere at a temperature of 90 ° C., and then 1.6 times in a hot air at a temperature of 250 ° C.
It was drawn twice to obtain a monofilament having a diameter of 2.2 mm. Details of the content of the nylon monomer residue (component) in the polyamide resin composition of this example are shown in Table-2.
6 nylon monomer residues were 79% by weight, 66 nylon monomer residues were 10% by weight, and 12 nylon monomer residues were 11% by weight.

The monofilament obtained in this example has a tensile strength of 7.4 g / d, the monofilament of Novamid 2420A alone has a tensile strength of 5.9 g / d,
The tensile strength of the monofilament made of Grillon CR8 alone was 6.5 g / d. Table 3 shows the strength ratio of the monofilament obtained in this example together with the tensile strength. A monofilament was produced using Novamid 2420A as a raw material in the same manner as above, and the maximum draw ratio that was possible was determined to be 5.6 times. The maximum draw ratio for Grilon CR8 was 6.8 times. Was.

[Examples 2 to 5, Comparative Examples 1 to 5] In the example described in Example 1, the polyamide B-1
The pellets of B-2 and the pellets of polyamides C-1 and C-2 were weighed and mixed at a ratio shown in Table 2, and a monofilament was produced in the same procedure as described in Example 1. Details of the content of the nylon monomer residue of the raw material polyamide resin composition are listed in Table 2, and the tensile strength of the obtained monofilament (a), the strength of the polyamide B only monofilament (b), and the polyamide C only monofilament Table 3 shows the intensity (c), the intensity ratio calculated from the formula (I), and the like.

[0032]

[Table 2]

[0033]

[Table 3]

[Examples 6 to 8] Monofilaments having different diameters by using the same resin composition as described in Example 1 and changing the extrusion amount by the same extruder used in the same example. , And the tensile strength (a) of the obtained monofilament, the strength (b) of the monofilament of only polyamide B-1 and the strength (c) of the monofilament of only polyamide C-1, similarly calculated from the above formula (I) Table 4 shows the obtained intensity ratios and the like.

[0035]

[Table 4]

The following is clear from Tables 2 to 4. (1) The polyamide resin composition for a high-strength monofilament according to the present invention is composed of a blend of two kinds of polyamide resins, and the monomer residues of the polyamide resin constituting the polyamide resin composition are combined in a specific ratio range. Therefore, a high-strength monofilament can be manufactured (see Examples 1 to 8). (2) On the other hand, if the monomer residue of the polyamide resin contained in the polyamide resin composition is out of the range essential in the present invention, the strength of the monofilament obtained from the polyamide resin composition is as described in Examples. Inferior to those (see Comparative Examples 1 to 5). (3) When the strength ratio of the monofilament obtained from the polyamide resin composition for a high-strength monofilament is less than 1.1, the strength of the monofilament is inferior to that of the examples (comparative). Example 1 to Comparative Example 5
reference).

[0037]

As described in detail above, the present invention has the following particularly advantageous effects, and its industrial value is extremely large. 1. The polyamide resin composition for a high-strength monofilament according to the present invention comprises at least two types of polyamide resins, and the monomer residues of nylon contained in the polyamide resin composition are combined in a specific range, so that it has been conventionally realized. A high-strength monofilament that could not be produced can be produced. 2. Since the high-strength monofilament obtained from the polyamide resin composition for a high-strength monofilament according to the present invention has a high strength, its diameter can be reduced, and when used for fisheries-related applications, it is stored in a narrow fishing boat. There is no need to reduce the space and the size of the gimmick, and the volume of fishing gear that can be carried on a fishing boat can be reduced, which can greatly contribute to downsizing of fishing gear. 3. Moreover, when the high-strength monofilament according to the present invention is used as a fishing line for longline fishing, the high-strength hardly causes breakage of the line, the diameter can be reduced, and the result is less noticeable in water. Absent.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Katsuhiko Sugiura 5-6-1 Higashi-Hachiman, Hiratsuka-shi, Kanagawa F-term in the Technology Center, Mitsubishi Engineering-Plastics Corporation (reference) 4J001 DA01 DB04 EA06 EA08 EA15 EA17 EB08 EC08 FA06 FB03 FC03 FD01 HA02 JA10 JB21 4J002 CL021 CL052 GA00 GC00 4L035 BB31 BB79 BB80 BB81 BB89 BB91 DD14 EE08 FF01 FF02 HH10 LC03 LC06

Claims (7)

[Claims] 1. A polyamide resin composition for a high-strength monofilament containing at least two kinds of polyamide resins having different compositions, wherein the polyamide resin composition has ε-
Add 7 caprolactam monomer residues (6 nylon components)
8.0 to 85.0% by weight of a polyamide-forming monomer residue consisting of adipic acid and hexamethylenediamine (66
1.0-15.0% by weight of nylon component) and ω
-Containing 3.0 to 22.5% by weight of laurolactam monomer residues (12 nylon components), and a total of three kinds of polyamide resin forming monomer residues being 100% by weight, Polyamide resin composition for high strength monofilament. 2. A polyamide resin composition comprising: a copolymerized polyamide (polyamide B) comprising ε-caprolactam, hexamethylenediamine and adipic acid; and a copolymerized polyamide (polyamide C) comprising ε-caprolactam and ω-laurolactam. The polyamide resin composition for a high-strength monofilament according to claim 1, which is a blend with (1). 3. Polyamide B is a copolymerized polyamide of ε-caprolactam, hexamethylenediamine and adipic acid, wherein the monomer residue is in a weight ratio of 95: 5 to 95: 5.
60:40, wherein the polyamide C is a copolymerized polyamide of ε-caprolactam and ω-laurolactam,
The polyamide resin composition for a high-strength monofilament according to claim 2, wherein the monomer residue has a weight ratio of 95: 5 to 75:25. 4. A high-strength monofilament produced from a polyamide resin composition containing at least two kinds of polyamide resins, wherein the polyamide resin composition has ε-
Add 7 caprolactam monomer residues (6 nylon components)
8.0 to 85.0% by weight of a polyamide-forming monomer residue consisting of adipic acid and hexamethylenediamine (66
1.0-15.0% by weight of nylon component) and ω
-A high-molecular weight resin containing 3.0 to 22.5% by weight of laurolactam monomer residues (12 nylon components), and a total of 100% by weight of three types of polyamide resin-forming monomer residues. Strength monofilament. 5. A polyamide resin composition comprising: a copolymerized polyamide (polyamide B) comprising ε-caprolactam, hexamethylenediamine and adipic acid; and a copolymerized polyamide (polyamide C) comprising ε-caprolactam and ω-laurolactam. 5. The high-strength monofilament according to claim 4, which is a blend with (1). 6. Polyamide B is a copolymerized polyamide of ε-caprolactam, hexamethylenediamine and adipic acid, wherein the monomers are in a weight ratio of 95: 5 to 6
The high-strength monofilament according to claim 5, wherein the polyamide C is a copolymerized polyamide of ε-caprolactam and ω-laurolactam, and the monomers are in a weight ratio of 95: 5 to 75:25. . 7. The tensile strength of a filament made of polyamide B is b, the tensile strength of a filament made of polyamide C is c, and the tensile strength of a filament made of a polyamide resin composition containing polyamide B and polyamide C is a. 7. The high-strength monofilament according to claim 5, wherein the strength ratio of a, b, and c satisfies the following formula (I). (Equation 1)