JPH0722475B2 - fishing line - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a fishing line, at least the surface of which is made of a polymer having a fluorinated alicyclic structure.

[Prior Art] Conventionally, nylon and the like have been used for fishing lines. In recent years, its strength, low refractive index, high light resistance and low water absorption have been evaluated, and polyvinylidene fluoride has been used as a material for fishing line.

However, the refractive index of polyvinylidene fluoride is 1.42, and a material having a sufficient strength and a lower refractive index has been desired.

[Problems to be Solved by the Invention] An object of the present invention is to newly provide a fishing line having an extremely low refractive index, which has never existed before.

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies based on the recognition of the above problems, and as a result, the polymer having a fluorinated alicyclic structure has high transparency and a low refractive index. It has been newly found that it is extremely advantageous as a material which has excellent moldability and gives a fishing line of sufficient strength.

Thus, the present invention has been completed based on the above findings, and provides a novel fishing line characterized in that at least the surface is made of a polymer having a fluorinated alicyclic structure.

In the present invention, the polymer having a fluorinated alicyclic structure can be exemplified in a wide range, including those conventionally known or well known. Therefore, in the present invention, a fluoropolymer having the above-mentioned specific ring structure in the main chain is preferably adopted.

For example, the general formula General formula And those having a ring structure. Of these, polymers having the following ring structures are typical. However, the contents of the present invention are not limited to these.

The methods for producing these polymers are as follows. However, it is not limited to these manufacturing methods.

1. By cyclopolymerization 2. Using cyclic monomers In the above, a polymer having a perfluoroaliphatic ring structure is exemplified, but in the present invention, a part of the above exemplified fluorine atoms is substituted with another hydrogen atom or an organic group, or by metathesis polymerization. can get And those having a ring structure such as

Thus, the polymer having a specific ring structure in the present invention can be smoothly and advantageously obtained by the cyclopolymerization as described above, and in particular, it has two polymerizable groups having different polymerizability in the molecule and By using a monomer having 2 to 7 atoms in the straight chain portion of the linking chain that connects these two polymerizable groups, it is possible to prevent gelation from occurring without using ultrahigh pressure conditions or large dilution conditions. It is possible to suppress the raw material and smoothly and advantageously proceed the cyclopolymerization.

As a monomer suitable for the cyclopolymerization as described above, first of all, it is desirable to have two carbon-carbon multiple bonds having different polymerizability. Usually a carbon-carbon double bond is employed. For example, a fluorine-containing monomer having two non-symmetrical multiple bonds, a vinyl group and an allyl group, a vinyl ether group and a vinyl group, a fluorine-containing multiple bond and a hydrocarbon multiple bond, a perfluoro multiple bond and a partially fluorinated multiple bond. It can be mentioned as. Secondly, it is desirable that the number of atoms in the linear portion of the connecting chain connecting these two carbon-carbon multiple bonds is 2 to 7. The number of atoms in the linear part of the connecting chain is 0
In the case of 1, cyclopolymerization hardly occurs, and in the case of 8 or more, the same is true. Usually, the number of atoms is preferably 2 to 5. Further, the connecting chain is not limited to a linear one, and may have a side chain structure or a ring structure, and the constituent atoms are not limited to carbon atoms, and may include hetero atoms such as O, S and N. . Thirdly, a fluorine content of 10% by weight or more is desirable. When the fluorine content is too low, it becomes difficult to exhibit the specificity of the fluorine atom. As a matter of course, a perfluoro monomer is preferably used.

Specific examples of the above specific fluorine-containing monomer, Etc. can be illustrated.

In the present invention, one having one vinyl ether group of CF ₂ = CFO-is preferably adopted in terms of polymerization reactivity, cyclopolymerization property, gelation suppression, and the like. In particular, perfluoroallyl vinyl ether (CF ₂ = CFOCF ₂ CF = CF ₂ ) and perfluorobutenyl vinyl ether (CF ₂ = CFOCF ₂ CF ₂ CF = C
F ₂ ) is mentioned as a suitable example.

The above-mentioned monomer components may be used alone or in combination of two or more, and further, they may be copolymerized in combination with other copolymer components so long as the essence of these components is not impaired. If desired, the polymer may be crosslinked by any method.

The other monomer to be copolymerized is not particularly limited as long as it is a monomer having radical polymerizability, a fluorine-containing system,
Hydrocarbons and others can be exemplified extensively. As a matter of course, one of these other monomers may be radically copolymerized with a monomer capable of introducing the specific ring structure alone, or two or more appropriate monomers may be used in combination to carry out the above copolymerization reaction. You can let me do it. In the present invention, it is usually desirable to select a fluorine-containing monomer such as fluoroolefin or fluorovinyl ether as the other monomer. For example, tetrafluoroethylene, perfluorovinyl ether, perfluoropropyl vinyl ether, or perfluorovinyl ether containing a functional group such as a carboxylic acid group or a sulfonic acid group is a preferable specific example, vinylidene fluoride, vinyl fluoride, Chlorotrifluoroethylene and the like are also exemplified.

As the copolymer composition, the composition of the cyclic structure is preferably 20% or more, more preferably 40%, in order to take advantage of the characteristics of the specific fluorine-containing alicyclic structure intended in the present invention.
The above is desirable.

In the present invention, as a method for crosslinking the fluoropolymer, a commonly used method or the like can be appropriately used. For example, a monomer having a cross-linking site may be subjected to co-polymerization for cross-linking, a cross-linking agent may be added for cross-linking, or radiation may be used for cross-linking.

In addition, various additives such as an antioxidant and an ultraviolet stabilizer may be added to the fluoropolymer in the present invention in order to improve practicality.

Since the polymer having a specific ring structure in the present invention can be used in a fluorine-based solvent or the like, it is also possible to form a thin protective film by dipping from a solution. Further, since the thermoplastic resin has a low melting temperature and a relatively low melt viscosity, the heat melting property is also good.

The solvent used is not limited as long as it dissolves the above-mentioned polymer, but perfluorobenzene, “Aflude” (trade name: fluorine-based solvent manufactured by Asahi Glass Co., Ltd.), “Fluorinert” (trade name: manufactured by 3M Company) (A liquid containing perfluoro (2-butyltetrahydrofuran)), trichlorotrifluoroethane and the like are preferable. Of course,
Appropriate two or more kinds can be used together as a solvent. Particularly in the case of a mixed solvent, hydrocarbons, alcohols and other organic solvents can be used together. Solution concentration is 0.01 wt% to 50
wt%, preferably 0.01 wt% to 20 wt%.

It is also possible to use a solution of the above polymer to coat a polyvinylidene fluoride fishing line.

[Operation] In the present invention, the polymer having a fluorinated alicyclic structure has low crystallinity or almost no crystallinity, and therefore exhibits high transparency and high light transmittance even though it is a fluororesin. Since it is a fluorine-containing polymer, it is considered that it has a lower refractive index than ordinary hydrocarbon resins and is excellent in moisture resistance, weather resistance and chemical resistance. However, it goes without saying that the above description is intended to help understanding of the present invention and does not limit the present invention.

[Examples] Next, examples of the present invention will be described more specifically, but it goes without saying that the description does not limit the present invention.

Synthesis Example 1 35 g of perfluoroallyl vinyl ether, 5 g of trichlorotrifluoroethane (hereinafter abbreviated as R113), 150 g of ion-exchanged water, and 35 of (C ₃ F ₇ COO) ₂ as a polymerization initiator.
mg was placed in a pressure-resistant glass autoclave with an internal volume of 200 ml.

After purging the system with nitrogen three times, suspension polymerization was carried out at 26 ° C. for 23 hours. As a result, 28 g of a polymer was obtained.

When the infrared absorption spectrum of this polymer was measured,
1660 cm _-1 , 1840c due to the double bond present in the monomer
There was no absorption near m _-1 . When this polymer was dissolved in perfluorobenzene and the ¹⁹ F NMR spectrum was measured, the spectrum showing the following repeating structure was obtained.

The intrinsic viscosity [η] of this polymer is "Fluorinert" FC-7
5 (trade name: a liquid containing 3M company perfluoro (2-butyltetrahydrofuran) as a main component, hereinafter abbreviated as FC-75), and was 0.530 at 30 ° C. The glass transition temperature of the polymer is 69 ° C., and it is a tough and transparent glassy polymer at room temperature. The 10% thermal decomposition temperature is 462 ℃, and the refractive index is
It was as low as 1.34 and the light transmittance was as high as 95%.

Synthesis Example 2 20 g of 1,1,2,4,4,5,5-heptafluoro-3-oxa-1,6-heptadiene and 40 g of R-113 were placed in a nitrogen-substituted three-necked flask and used as a polymerization initiator. (C ₃ F ₇ COO) ₂ 20m
After adding g and purging the system with nitrogen, polymerization was carried out at 18 ° C. for 10 hours. As a result, 10 g of a polymer was obtained. This polymer was a polymer soluble in R-113 and had an intrinsic viscosity "η" of 0.96 in meta-xylene hexafluoride at 30 ° C. It was confirmed by ¹⁹ F and ¹ H NMR that the polymer had a ring structure in the main chain.

The polymer was colorless and transparent, and had a low refractive index of 1.36 and a high light transmittance of 93%.

Synthesis Example 3 30 g of perfluoroallyl vinyl ether, 5 g of trichlorotrifluoroethane (hereinafter abbreviated as R113), 150 g of ion-exchanged water, and 35 of (C ₃ F ₇ COO) ₂ as a polymerization initiator.
mg was put into a pressure-resistant autoclave having an internal volume of 200 ml.

After replacing the system with nitrogen three times, vinylidene fluoride 12g
Was introduced and suspension polymerization was carried out at 26 ° C. for 23 hours. as a result,
28 g of a polymer was obtained.

The refractive index of the polymer was 1.38.

Synthesis Example 4 35 g of perfluorobutenyl ruvinyl ether, 5 of R113
g, 150 g of ion-exchanged water, and 90 mg of diisopropyl peroxydicarbonate as a polymerization initiator, the internal volume of 200 m
It was placed in a pressure-resistant glass autoclave of l.

After purging the system with nitrogen three times, suspension polymerization was carried out at 40 ° C. for 23 hours. As a result, 28 g of a polymer was obtained.

When the infrared absorption spectrum of this polymer was measured,
1660 cm _-1 , 1840c due to the double bond present in the monomer
There was no absorption near m _-1 . Further, this polymer was soluble in perfluorobenzene, aflude and fluorinate. Further, when the ¹⁹ F NMR spectrum was measured, a spectrum corresponding to the ring structure was obtained as in Synthesis Example 1.

The intrinsic viscosity “η” of this polymer was 0.50 at 30 ° C. in FC-75. The glass transition point of the polymer is 110 ° C., and it is a tough and transparent glassy polymer at room temperature. The 10% thermal decomposition temperature was 465 ° C. The water absorption rate was 0.01% or less, the dielectric constant at room temperature was 2.2 (60Hz to 1MHz), and the volume resistance was ¹⁷ or more.

The refractive index of the polymer was 1.34.

Examples 1 to 4 Transparent spinning yarns were obtained by melt spinning using the polymers obtained in Synthesis Examples 1 to 4.

The strength of the obtained yarn was 300 to 350 kg / cm ² .

Example 5 The FC-75 solution of the polymer obtained in Synthesis Example 1 was used to coat the surface of a fishing line made of polyvinylidene fluoride. The obtained fishing line had a refractive index lower than that of the polyvinylidene fluoride fishing line, and was almost invisible in water.

[Advantages of the Invention] The present invention has an excellent effect of obtaining a fishing line having a low refractive index, high strength and good light resistance by employing a polymer having a fluorinated alicyclic structure as a material, and particularly, A substance having a high fluorine content also has an effect of having heat resistance, chemical resistance, moisture resistance, and stain resistance.

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Claims (4)

[Claims] 1. A fishing line, at least the surface of which is made of a polymer having a fluorinated alicyclic structure. 2. The fishing line according to claim 1, wherein the polymer having a fluorinated alicyclic structure is a polymer having a ring structure in the main chain obtained by cyclopolymerization. 3. The fishing line according to claim 1, wherein the entire thread is a polymer having a fluorinated alicyclic structure. 4. The fishing line according to claim 1, which is obtained by coating a polymer having a fluorinated alicyclic structure.