JPS6017845B2 - Vinylidene fluoride resin monofilament - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a monofilament molded from a vinylidene fluoride resin composition.

More specifically, it takes advantage of polyvinylidene fluoride resin's high specific gravity, high strength, and excellent transparency, and also provides long-lasting flexibility and impact breakage resistance, making it especially ideal for fishing lines. This relates to a monofilament having the following characteristics. Monofila mesoto used as a fishing line ranges from 0.3 to 1.8 with an average thread diameter of 90 microns.
There are various types such as 5mm thread No. 12, and most of them are nylon threads. As is well known, nylon thread has high strength and appropriate flexibility, and has excellent properties as a fishing line, but on the other hand, it has disadvantages such as absorbing water and reducing strength, short durability, and low specific gravity. have In particular, the low specific gravity means that fishing lines tend to float on the surface of the water and have a slow settling speed, which can cause the lines to become entangled, making it difficult to reach the desired fishing spot quickly. These drawbacks become noticeable when tuna is used as a very thick monofilament, commonly known as ``sekiyama'' or ``tsurimoto'' in the longline fishing method. Conventionally, longline fishing methods used ``sekiyama'' or ``tsurimoto.'' Three strands of wire was used as the thread, but it was changed to three strands of nylon No. 4 thread because it was difficult to handle, such as being curly, too heavy, and prone to rust. The twisted thread is easy to handle due to the flexibility peculiar to synthetic resin, and the fishing rate is improved, which seems to be a result of its transparency. In addition, nylon No. 12 monofilament is being used.According to the opinions of field operators, this No. 12 monofilament has a smoother surface and better transparency compared to 3-strand strands, which further improves the fishing rate and makes it easier to handle. He says it's gotten easier.

However, since nylon thread has a low specific gravity of 1.13 to 1.15, it tends to float on the sea surface and become tangled when fishing.
The drawback is that it does not reach the tuna swimming area 40 to 50 meters below the sea surface quickly, which prevents it from being very effective as an extra-thick monofilament.

Furthermore, in the tuna longline fishing method, the fishing line is left in seawater for several hours to a day and night, so the strength of the nylon decreases by 10 to 40% due to water absorption, making it unreliable as a fishing line. . The inventors of the present invention took advantage of the transparency and flexibility of nylon thread, which increases the chance of missed catches, and made extensive studies to create a fishing line that improves the above disadvantages.
This provides a completely new, ideal fishing line that has excellent tensile strength, durability, impact breakage resistance, and flexibility with a high sedimentation rate. That is, the present invention uses a copolymer of methyl acrylate and isobutylene containing 15 wt. 3
parts by weight and 1 to 1 part by weight of a polyester plasticizer are added to form a melt-grade yarn, which is then hot-stretched to give it flexibility that can be maintained over a long period of time. Vinylidene fluoride resin has high crystallinity and a large intermolecular cohesive force, so the elastic modulus of the drawn thread is 250 to 350 kg/m, making it stiff, which is good for thin filaments with a small thread diameter, but tuna It is not easy to handle it as a very thick monofilament with a diameter of 0.08 willow or more, which is used in long-line fishing. As a method of imparting flexibility, there is a polyprend of compatible plasticizers or other polymers, but vinylidene fluoride resins such as those mentioned above have poor adhesion and blendability with plasticizers, polymers, auxiliary agents, etc. Unfortunately, it has the disadvantage that it is difficult to mix well with these.

As practical compatible plasticizers, only US Pat. No. 354,103y and JP-A-501111147 are known. The former is an acid with 4 to 8 carbon atoms and an acid with 4 to 8 carbon atoms.
A polyester with a molecular weight of 1,100 to 5,000, consisting of an alcohol with a carbon number of 7 to 5,000; It is a polyester consisting of monovalent acid or monovalent alcohol residues and having a molecular weight of 1,500 to 4,000.

However, the flexibility targeted by the present invention has an elastic modulus of 120~
60k9/mau is required, and in order to obtain this elastic modulus, it is necessary to mix the above-mentioned polyester plasticizer in an amount of 1 cloud part or more.

Even if a plasticizer is compatible with vinylidene fluoride resin, if it is added in an amount of 7 parts by weight or more, bubbles will inevitably be mixed into the filament during production. It is impossible to maintain flexibility over a long period of time, and the tensile strength is greatly reduced, making it impractical.Of course, tensile strength is required in the longline fishing method for tuna. -Resins that have good compatibility with polyvinylidene fluoride resin include polymethyl methacrylate resin proposed by the Japanese Patent Publication No. 12012/1983, and Japanese Patent Application Laid-open No. 116538/1983;
Polymethyl acrylate and copolymers of methyl acrylate and isobutylene proposed in Japanese Patent Nos. 50-116582 and 50-116583 are exceptionally known.

However, polymethyl methacrylate resin has a glass transition temperature of T
Tg-3 of vinylidene fluoride resin with g of 80 to 100 0
8oo, these polyprend molded products become hard and brittle over time, and cannot be imparted with flexibility. In addition, when polymethyl acrylate or a copolymer of methyl acrylate and isobutylene is blended, the elastic modulus can be reduced to 120 kg/mau or less by adding about 3 parts by weight or more to 10 parts by weight of polyvinylidene fluoride. However, it has the disadvantage that the tensile strength decreases more markedly than when a plasticizer with good compatibility is added, and the generation of bubbles is unavoidable during filament production.
As a fishing line, the higher the strength, the better, and it is necessary to minimize the decrease in strength by imparting flexibility, which cannot satisfy the purpose of the present invention. However, when the polyester plasticizer is used in combination with polymethyl acrylate or a copolymer of methyl acrylate and isobutylene in a certain amount, the elastic modulus can be increased to 12.
Filaments with a density of 0k9/m or less can be manufactured without introducing bubbles, yet no plasticizer leakage is observed, the decrease in tensile strength is extremely small, and the impact rupture resistance is dramatically improved. It improves.

In order to achieve the target elastic modulus of 120 to 60 k9/hiro and tensile strength of 30 k9/m or more, the above acrylate resin should be added in an amount of 1 to 3 parts by weight, preferably 5 to 1 part by weight.
5 parts by weight of the polyester plasticizer and 1 to 1 part by weight, preferably 2 to 7 parts by weight, and if one is relatively small within this range, the other is a relatively large amount of vinylidene fluoride. It may be added to the weight part of the system resin 10.

Furthermore, the combined use of the acrylate resin and the polyester plasticizer has the effect of increasing the thread fluidity of the polyblend resin, and can also improve processability. In order to dramatically improve the impact rupture resistance, which is another object of the present invention, the amount of the acrylate resin and the polyester plasticizer to be added to 10 parts by weight of the vinyl fluoride IJ-density resin is as follows. Within this range, the amount of the acrylate resin added is greater than the amount of the polyester plasticizer, preferably at least twice the amount of the polyester plasticizer.

Mechanical mixing of vinylidene fluoride resin and polymethyl acrylate resin or copolymer of methyl acrylate and isobutylene using an ordinary blender is also possible, but these acrylate resins have a low Tg. Therefore, it is rubbery and clumpy and may be difficult to mix.

In such cases, the acrylate monomers can be reliably dispersed by adsorption polymerization in the vinylidene fluoride resin particles using a so-called intra-particle post-polymerization product. The amount of adsorption polymerization of acrylate monomer per 10 parts by weight of vinylidene fluoride resin obtained by suspension polymerization is as much as 15 parts by weight, and these polymerized particles are usually used to adjust the amount according to the purpose. Dispersion mixing can be performed using a blender.

The vinylidene fluoride resin composition according to the present invention is melt-drawn and hot-stretched in a conventional manner.

To describe a specific example of the spinning method, the resin composition of the present invention, which has been plasticized by an extruder, is extruded from a nozzle through a gear pump and rapidly cooled.

The temperature of the molten resin is higher than the melting point (approximately 17 mm) or higher than the thermal decomposition temperature (
It is possible to use any temperature below 350 qo), but 20
0 to 300 is preferable. Water is usually used for the quenching, but the temperature is preferably below 50 mm, preferably below 50 psi, at which no bubbles are generated due to boiling at the interface with the molten resin. The undrawn yarn thus crystallized and solidified is then preheated in a heat medium of 80 to 120 qo, and then heated in a heat medium of 150 to 165°C for 4.
Stretched by 0 to 5.3%, and then stretched to 160 to 165q0
Stretched to 1.1 to 1.2 times in a heating medium, and then stretched to 80 to 1.2 times.
It is subjected to a 5-20% relaxation heat treatment in dry heat at 160°C and rolled up. The heating medium may be any one having a boiling point of 170° C. or higher and chemically inert to the resin composition of the present invention, such as silicone oil, liquid paraffin, glycerin, etc., but preferably glycerin, which allows the drawn yarn to be washed with water.

Further, the stretching temperature and magnification can be appropriately selected depending on the resin composition of the present invention so as to increase the strength development. The drawing speed greatly affects the quality of the yarn, especially the strength, and the slower the drawing speed, the greater the strength development.
~20 skin min. The vinylidene fluoride resin of the present invention is a vinylidene fluoride homopolymer, a copolymer containing 70 mol% or more of vinylidene fluoride as a constituent monomer, which is physically and chemically similar to the homopolymer, or a copolymer containing any of these. It is a blend of

Here, the copolymer includes, for example, ethylene tetrafluoride, ethylene monochloride trifluoride, which can be copolymerized with pinylidene fluoride monomer,
Copolymers containing up to 5 mol % of halogenated ethylene such as propylene hexafluoride and vinyl fluoride are preferably used. As the polyester plasticizer used in the present invention, any polyester plasticizer can be used as long as it has good compatibility with the pinylidene fluoride resin.

Among them, the repeating unit composition is an ester of a dialcohol having 2 to 4 carbon atoms and a dicarboxylic acid having 4 to 6 carbon atoms, and the terminal group is 1 to 3 carbon atoms, as disclosed in JP-A-50-111147. Polyesters consisting of monovalent acid groups or monovalent alcohol residues and having a molecular weight of 1,500 to 4,000 are particularly preferably used. The yarn thus obtained has a high specific gravity of 1.65 to 1.83, is highly strong, flexible, and has good transparency.

In particular, it has a thread thickness of 0.08 to 2, and a tensile strength of 30k9/
Those having an elastic modulus of 60 to 200k9/fence can be effectively used in the tuna longline fishing method. The present invention will be explained in detail below with reference to Examples.

Example 1 Inherent viscocity obtained by suspension polymerization (solvent: dimethylformamide, concentration: 0.
4 t/d' at a temperature of 30 qo) is 1.30 d'
A dispersion polymer was obtained by adsorbing 6 parts by weight of methyl acrylate to 100 parts by weight of polyvinylidene fluoride (PVDF) particles. PV in 33 parts of this type of polymer
By adding 79.5 parts of DF, a mixture of 12.5 parts by weight of PVDFIO and 12.5 parts by weight of polymethyl acrylate resin is obtained.

This mixture was mixed with 5 parts by weight of a polyester having a molecular weight of 2,100, which was obtained by acetylating the end groups of an ester of propylene glycol and adipic acid, to obtain a composition as a melt-extruded pellet. This is processed using a 304 extruder at a resin temperature of 26
Melt spun at 0°C and quenched in water at 50°C, followed by 1
Stretched to 5.2 times in 60"0 glycerin, and further stretched to 16"
The monofilament was drawn in 5 qo glycerin at 1.1 kawabe in two stages, and then relaxed by 10% in 85 q0 hot air to obtain a monofilament with an L yarn diameter of 1.75.

This monofilament has excellent transparency and flexibility,
The fiber has a tensile strength of 50k9 and a specific gravity of 1.7u and a refractive index of 1.
44 initial elastic modulus was 120k9/fence, and impact resistance to breakage energy was 280k9 per arc. Here, the impact rupture energy is measured by the following method. That is, one end of the system of sample length L is attached to a stopper, and the weight is allowed to fall naturally from the stopper towards the position of the skin of L.

At this time, the weight of the weight was varied depending on the difference in △W, and each weight was tried n times to determine the number of times the yarn was broken or not, and the impact breaking energy was determined using the following formula. Impact breaking energy: L{Wmax-△W)} Here, n=5 Wmax: n=5 Weight when all of them break Nx: Total number of broken threads during the test The speed of sedimentation of this thread in seawater is It settled in 15 seconds at a depth of 2 hours, and there was no change in strength and elongation even after being immersed in seawater for 2 days and nights.

In contrast to the monofilament according to the present invention, the nylon thread with a thread diameter of 1.85 mm used in the tuna longline fishing method has a tensile strength of 38 kg/rock, but the sedimentation speed in seawater is 9. Tensile strength after immersion in seawater for 24 hours decreased by 25% to 28.5k9/shore.

Example 2 Inherent viscocity obtained by suspension polymerization 1.3
Methyl acrylate monomer and isobutylene monomer to PVDFIO blood weight part of 0d'/night 9 village 1
A spherical polymer was obtained by adsorbing and intraparticle polymerizing a total of 3 parts by weight of both in a ratio of 0 to PVDF particles.

This kind of polymer43. A mixture of parts by weight of PVDFIO and parts by weight of methyl acrylate-isobutylene copolymer 1 was obtained by mixing $ parts with 66.7 parts of PVDF. The composition was obtained as a melt extruded pellet. Example 1
A monofilament having a yarn diameter of 1.0 and excellent transparency was obtained by drawing the fused paper yarn by the method described in .

This thread has a specific gravity of 1.710 and a tensile strength of 53.5k9nomatsu.
It was a flexible and strong yarn with an initial elastic modulus of 100k9/rail, a refractive index of 1.42, and an impact breaking energy of 130k9. The sedimentation speed of this yarn was 15 seconds to a water depth of 2, and there was no change in strength and elongation over time in seawater after 4 gluing hours.

Example 3 15 parts by weight of methyl polyacrylate was pulverized into particles by freeze-pulverization based on parts by weight of PVDFIO having an independent viscocity of 1.30 obtained by suspension polymerization, and the polyester of Example 1 5 parts by weight of plasticizer are cold mixed.

A rather coarsely granular composition is obtained. This composition was obtained as a melt extruded pellet.

By drawing the fused paper yarn using the method described in Example 1, a filament with a yarn diameter of 1.2 and excellent transparency was obtained. This yarn has a specific gravity of 1.70, a tensile strength of 40k9/ground, an initial modulus of elasticity of 80k9, and an impact breaking energy of 165k9.
It was a strong thread that was incredibly flexible. Example 4 The terminal group was acetylated with an ester of butanediol and adipic acid as a plasticizer, and 2 parts by weight of polyester with a molecular weight of 1600 and 15 parts of methyl acrylate-isobutylene copolymer were added.
As a result of carrying out the same procedure as in Example 2 except that the weight part was used, a filament with excellent transparency and a thread diameter of 1.6 was obtained.

This yarn has a tensile strength of 38k9/m and an initial modulus of elasticity of 115k9.
It is a flexible and strong yarn with an impact breaking energy of 210k9. Example 5 Inherent Viscocity 1.
A highly transparent filament with a thread diameter of 1.4 ribs was obtained by carrying out the same procedure as in Example 2 except that 6 parts by weight of the polyester plasticizer was used with respect to 45 parts by weight of PVDF IOO.

This thread has a tensile strength of 44k9/secret and an initial elastic modulus of 90kg/
It is a flexible thread with an impact breaking energy of 150k9-arc. Example 6 In-hear sotopiscocity 1.80d'/evening PVD
In the FIOO parts by weight particles, methyl acrylate monomer and imbutylene monomer were polymerized within the adsorbed particles at a ratio of 9 to 10 by weight, totaling 10 parts by weight, to obtain a spherical polymer.

Add 35 parts of this polymer to 1.80 d'/Yu no PVD.
Nota's PVDF21 with F61.4 part and skin 0.85
．． A mixture of 1 part by weight of PVDFIOO and 17.5 parts by weight of methyl acrylate-isobutyl copolymer was obtained by mixing with 1 part by weight of PVDFIOO, and 6.5 parts by weight of the polyester plasticizer described in Example 1 was further mixed to obtain the composition. A pellet was obtained by melt-extruding the product. Then, by the method described in Example 2, molten iron thread,
By drawing, a monofilament with a thread diameter of 1.6 ribs and excellent transparency was obtained. This yarn was a flexible, strong yarn with a tensile strength of 36 kg/K, an initial elastic modulus of 75 K9, and an impact breaking energy of 270 K9. Comparative Example 1 A filament with a yarn diameter of 0.5 was obtained in the same manner as in Example 1 except that neither a plasticizer nor methyl polyacrylate was used.

The yarn has a tensile strength of 70k9/rail, and an initial elastic modulus of 270k9/
The impact rupture energy was 30k9. Comparative Example 2 A filament with a yarn diameter of 1.2 was obtained in the same manner as in Example 1 except that polymethyl acrylate was not used.

The yarn has a tensile strength of 62kg/rail, and an initial elastic modulus of 140k9/
The fence had an impact rupture energy of 135k9-arc. Comparative Example 3 The same procedure as in Example 1 was carried out except that methyl polyacrylate was not used and the plasticizer was used in an amount of 12.5 parts by weight. A filament that is easy to break was obtained.

When we dared to examine the fiber quality in areas that did not contain air bubbles, we found that the tensile strength was 28k9/bar, the initial elastic modulus was 90k9/m, and the impact rupture energy was 120k9 per arc. Comparative Example 4 The same procedure as in Example 2 was carried out except that no plasticizer was used and the copolymer of methyl acrylate and isobutylene was used as 1 part by weight. A filament was obtained that was prone to breakage and breakage.

When we dared to examine the quality of the fibers in areas that did not contain air bubbles, we found that the tensile strength was 67k9/fence and the initial elastic modulus was 200k9/m.
Comparative Example 5 The same procedure as in Example 2 was carried out except that no plasticizer was used and the copolymer of methyl acrylate and isobutylene was used in an amount of 3 parts by weight. A filament which was easily broken due to frequent occurrence of thread breakage was obtained.

When we dared to examine the yarn quality in the part that did not contain air bubbles, we found that the tensile strength was 25k9/ground, the initial elastic modulus was 100k9/fence, and the impact breaking energy was 130k9/fence. Comparative Example 6 The same procedure as in Example 2 was carried out except that the copolymer of methyl acrylate and isobutylene in Example 2 was changed to 35 parts by weight. Obtained a filament that was easy to use.

When we dared to examine the fiber quality in areas that did not contain air bubbles, we found that the tensile strength was 18k9/iso, the initial elastic modulus was 48k9/kyo, and the impact rupture energy was 125k9-low. Comparative Example 7 A filament was carried out in the same manner as in Example 2 except that the plasticizer was changed to 12.5 parts by weight, and a filament with a thread diameter of 1.3, which produced many bubbles and was easily broken, was obtained.

Claims (1)

[Scope of Claims] 1. 1 to 30 parts by weight of a methyl acrylate-isobutylene copolymer containing 15% by weight or less of polymethyl acrylate or isobutylene based on 100 parts by weight of vinylidene fluoride resin, and 1 to 10 parts by weight of a polyester plasticizer. The polyester plasticizer is composed of an acid having 4 to 8 carbon atoms and an alcohol having 4 to 7 carbon atoms, and the molecular weight is 1100 to 50.
00 polyester or an ester of a dialcohol having 2 to 4 carbon atoms and a dicarboxylic acid having 4 to 6 carbon atoms, the terminal group is composed of a monohydric acid or monohydric alcohol residue having 1 to 3 carbon atoms, and the molecular weight A filament obtained by melt-spinning and hot-stretching a polyester having a diameter of 1,500 to 4,000 and a filament diameter of 0.08 mm or more and a tensile strength of 30 kg.
/mm^2 or more, and a vinylidene fluoride resin monofilament having an elastic modulus of 60 to 120 kg/mm^2. 2. The fluorination according to claim 1, characterized in that the methyl acrylate-isobutylene copolymer is obtained by intraparticle polymerization of methyl acrylate-isobutylene monomers within polyvinylidene fluoride particles. Vinylidene resin monofilament.