JPH0314923B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to polyamide monofilaments. Specifically, the present invention relates to a polyamide monofilament with excellent transparency, flexibility, and strength. [Prior art] Polyamide monofilament is used for fishing nets, fishing nets,
It is often used in things like gatsuto. Strength is still an important characteristic required for fishing nets, but transparency and flexibility are equally required. For this reason, in addition to the usual polycapramide (nylon-6), polyamides made by copolymerizing caprolactam and adipate hexamethylene diammonium salt (nylon-6/66) or polyamides made of a blend of nylon-6 and nylon 6/66 are used. Monofilament has come into use. However, even when using nylon 6/66, the transparency and flexibility of thick monofilaments with a diameter of 1 mm or more, such as tuna stem thread, were insufficient, and the results were not satisfactory. [Purpose of the Invention] The present inventors have conducted extensive research in order to obtain a polyamide monofilament with excellent transparency, flexibility, and strength. As a result, by producing a polyamide monofilament using a specific polyamide as a raw material, transparency and flexibility can be improved. The present invention was completed based on the discovery that an improved polyamide monofilament can be obtained. In other words, the present invention has excellent properties, especially diameter
The purpose is to produce a polyamide monofilament that is highly valuable for use in thick monofilaments of 0.5 mm or more, and the purpose is to add aliphatic diamine and 100 parts by weight of polyamide (a) whose main component is caprolactam. Polyamide (b) whose main component is isophthalic acid and/or terephthalic acid
This can be achieved by producing a composition containing 0.5 to 20 parts by weight of ε-caprolactam and/or bisamide as a raw material. Further, the filament can be suitably produced by stretching under specific conditions. [Structure of the Invention] The present invention will be described in detail below. The polyamide (a) used in the present invention contains ε-caprolactam as a main component, that is, 50% by weight.
A nylon 6/66 copolymer is used, which is a polymer containing the above components and whose other copolymerization components are salts of hexamethylene diamine and adipic acid. especially,
Those with a 6/66 ratio of 95/5 to 70/30 are excellent. Further, it is preferable to use one having a relative viscosity of about 2.0 to 6.0, preferably about 3.0 to 5.0, as measured in accordance with JIS-K-6810. If the amount of adipic acid hexamethylene diammonium salt component in the copolyamide is too large, the strength will decrease. On the other hand, if it is too small, transparency and flexibility cannot be obtained. The polyamide (b) used in the present invention is one whose main components are aliphatic diamine and polyamide components of isophthalic acid and/or terephthalic acid.
It is a polyamide resin obtained by copolymerizing a polyamide component optionally consisting of lactam and/or aliphatic diamine and aliphatic dicarboxylic acid. The aliphatic diamines used in the production of such polyamide resins include linear aliphatic diamines such as ethylene diamine, tetramethylene diamine, hexamethylene diamine, octamethylene diamine, and decamethylene diamine, and their methylated, ethylated, and halogenated derivatives. can be mentioned. Furthermore, lactams include caprolactam, lauryllactam, and the like. Furthermore, as aliphatic dicarboxylic acids, succinic acid,
Examples include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and derivatives thereof such as methylated, ethylated, and halogenated products. In such polyamide (b), the polyamide component composed of lactam and/or aliphatic diamine and aliphatic dicarboxylic acid as a copolymer composition is 40% by weight.
If the content exceeds 20% by weight, the transparency decreases, so the content of such components is preferably 40% by weight or less, more preferably 20% by weight or less. Further, isophthalic acid and terephthalic acid can be used in any ratio, but preferably isophthalic acid/terephthalic acid = 80/20 to 20/80 (weight ratio). The method for producing polyamide (b) containing aromatic dicarboxylic acid as a main component is usually by adding a lactam to a nylon salt consisting of diamine and dicarboxylic acid, or an aqueous solution thereof, by a so-called melt polymerization method. However, depending on the composition of isophthalic acid and terephthalic acid, it can be produced by a solution method or an interfacial method. The polyamide resin used in the present invention preferably has a relative viscosity of ηrel=1.4 to 3.5 dl/g when measured at 25° C. using 98% concentrated sulfuric acid at a concentration of 1 g/dl. The blending amount of polyamide (b) is polyamide (a)
0.5 to 20 parts by weight, preferably 1 to 100 parts by weight
15 parts by weight. If the amount is too small, there will be no transparency improvement effect, and if the amount is too large, the flexibility and strength will deteriorate. In the present invention, ε-caprolactam and/or a bisamide represented by the general formula below can be further blended into the composition consisting of polyamides (a) and (b), if necessary. ε-caprolactam is a polymerization raw material for nylon 6, and a considerable amount remains as an unreacted monomer in nylon 6 immediately after polymerization, and it is usually reduced to 0.5
After extraction treatment is performed so that the residual amount is less than % by weight, it is subjected to melt spinning. Therefore, in the present invention, when the residual amount in the polymer is large, the total amount of the remaining ε-caprolactam and the added ε-caprolactam may be within the following blending range. Epsilon-caprolactam is preferably added in an amount of 5 to 20 parts by weight, particularly 7 to 18 parts by weight, per 100 parts by weight of the composition of polyamides (a) and (b). If it is too little, there will be no flexibility improvement effect, and if it is too much, kneading will be poor and stable spinning will not be possible. The bisamide compound used in the present invention has the general formula or (In the formula, R ¹ is a divalent hydrocarbon residue, R ² and R ³
represents a monovalent hydrocarbon residue, and R ⁴ and R ⁵ represent a hydrogen atom or a monovalent hydrocarbon residue. ) is a compound represented by Specifically, in the formula, R ¹ represents an alkylene group, an arylene group, an arylene dialkylene group, a diarylene realkylene group, etc., and R ² and R ³ represent an alkyl group, an aryl group, an aralkyl group, an alkaryl group, or a cycloalkyl group. R ⁴ and R ⁵ each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkaryl group, or a cycloalkyl group. More specifically, R ¹ is a methylene group,
Alkylene groups having 1 to 12 carbon atoms such as ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene; arylene groups such as phenylene and naphthylene; xylylene Examples thereof include an arylene dialkylene group in which two hydrogen atoms of an aromatic hydrocarbon are substituted with two alkylene groups, and a diarylene realkylene group such as a diphenylene trimethylene group. R ² and R ³ are ethyl group, butyl group,
Pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group , alkyl groups having 2 to 30 carbon atoms such as docosyl, heptacosyl and triaconcyl groups, aryl groups such as phenyl and naphthyl groups, aralkyl groups such as benzyl and phenylethyl groups, tolyl and ethylnaphthyl groups. Examples include alkaryl groups such as cycloalkyl groups such as cyclohexyl groups, and cycloalkyl groups such as cyclohexyl groups. R ² and R ³ may be the same group or different groups. R ⁴ and R ⁵ are hydrogen atoms, alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, and dodecyl, phenyl, and naphthyl. Examples include aryl groups such as benzyl groups, aralkyl groups such as phenylethyl groups, alkaryl groups such as tolyl groups and ethylnaphthyl groups, cycloalkyl groups such as cyclohexyl groups, etc., and R ⁴ and R ⁵ may be the same group or different groups. These R ¹ to R ⁵ groups may have a branched chain. The bisamide compound represented by the above general formula [] contained in the composition of the present invention includes alkylene diamines such as ethylenediamine, propylene diamine, butylene diamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, and dodecamethylene diamine; Diamines such as arylene diamines such as nylene diamine and naphthylene diamine; arylene dialkylene diamines such as xylene diamine; and stearic acid,
Alkylene bis fatty acid amides and arylenes obtained by reaction with fatty acids such as hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, arachidic acid, behenic acid, oleic acid, elaidic acid, and montanic acid. It refers to all bis fatty acid amides and arylene dialkylene bis fatty acid amides, but typical examples include N,N'-methylenebisstearic acid amide and N,N'-ethylenebisstearic acid amide. Bisamide compounds represented by the general formula [] include alkylamines such as ethylamine, methylamine, butylamine, hexylamine, decylamine, pentadecylamine, octadecylamine, and dodecylamine; arylamines such as aniline and naphthylamine; benzylamine, etc. aralkylamines; cycloalkylamines such as cyclohexylamine; monoamines such as terephthalic acid, p-phenylene dipropionic acid, succinic acid,
Refers to everything obtained by reaction with dicarboxylic acids such as adipic acid, among others, N,
N'-dioctadecyl terephthalic acid amide, N,
N'-Diethylenedioctadecyl terephthalic acid amide, N,N'-dioctadecyl-p-phenylene dipropionic acid amide, N,N'-dioctadecylsuccinic acid amide, N,N'-dioctadecyl adipic acid amide, N , N'-dimethyldioctadecyl adipate amide, etc. are representative examples. These bisamide compounds have the general formula [],
The compounds represented by [ ] may be used alone or as a mixture. The amount of bisamide added is 0.1 to 0.5 parts by weight, particularly 0.15 to 0.5 parts by weight, per 100 parts by weight of the composition of polyamides (a) and (b).
0.4 part by weight is preferred. If the amount is too large, white spots may occur in the monofilament due to poor kneading, or stable spinning may become impossible. If it is too small, the effect of improving transparency and flexibility will be small. ε-caprolactam and bisamide may be used together or either one of them may be used. Furthermore, in order to achieve the object of the present invention, a monofilament can be suitably produced by using the above composition and using the following manufacturing conditions. Melt spinning can be carried out using conventional methods and conditions, ie, by spinning from a nozzle in an extruder at a temperature range of 5 to 60° C. higher than the melting point of the polyamide polymer. Immediately after melt-spinning, it is cooled with water at 25°C or lower, but transparency deteriorates when the temperature is high, and transparency is good at a temperature range of 1 to 15°C. Next, the film enters the first stretching step, and the temperature in this step is the most important point in terms of manufacturing conditions for achieving both transparency and flexibility, which is the objective of the present invention. The stretching temperature in this step is 0°C to 100°C, more preferably 30°C to 100°C. Note that air,
The water may be water, hot water, steam, etc., and the type does not matter. Preferably hot water or steam. In addition, the stretching ratio at that time is preferably 3.0 to 5.0 times; if it is too high or too low, the strength will decrease and stable stretching will not be possible. The stretching conditions and annealing conditions for the subsequent second stage may be within a range that does not impair transparency and flexibility within the conditions for normal polyamide monofilament, and the second stage stretching is performed in heated air at 250 to 350°C. 1.1~
It is sufficient to adopt a stretching condition of 2.0 times and a relaxing condition of 0.9 to 1.0 times in heated air at 250 to 350° C. for annealing. Thus, the polyamide monofilament obtained by the present invention is a monofilament that has both excellent transparency and flexibility that could not be obtained conventionally, and can be used in various fields such as spinning for fishing, trunk yarn, and raw yarn for rope. Expected to be applied. [Example] Hereinafter, the present invention will be explained in detail with reference to Examples. Reference Example 1 Production of polyamide (b) 11.0 g of acetic acid was added to a salt aqueous solution consisting of 90% aqueous solution of Γ hexamethylene diamine 2.28 Kg, 9.0 Kg of Γ water, 1.96 Kg of Γ isophthalic acid, and 0.98 Kg of Γ terephthalic acid, and the mixture was placed in a reaction tank equipped with a stirrer. After preparation and sufficient _N2 substitution, 18
Heat and pressurize until the system pressure reaches Kg/ ^cm2 ,
After reaching 18 Kg/cm ² , the system was stirred while releasing the pressure to 18 Kg/cm ² to start the polymerization reaction. During this time, the internal temperature rose slowly to 210°C, and after 5 hours, almost no water was distilled out, and at this point the internal temperature indicated 250°C. The pressure was further released, and after the system pressure was finally reduced to 700 mmHg, pressure was returned to the reactor, and the molten polymer was extracted from the bottom of the reaction tank. This polymer is a polyamide resin containing 100% by weight of polyamide-forming components from aliphatic diamine, isophthalic acid, and terephthalic acid, and has a relative viscosity of ηrel.
was 2.1. This polyamide resin is designated as b-1. Reference Example 2 Production of polyamide (b) 11.0 g of acetic acid was added to a salt aqueous solution consisting of 90% aqueous solution of Γ hexamethylene diamine 2.28 Kg 9.0 Kg of Γ water 1.96 Kg of Γ isophthalic acid 0.98 Kg of Γ terephthalic acid 0.77 Kg of Γ caprolactam, and a stirrer was added. After filling the reactor with water and replacing it with enough _N2 , 18
Heat and pressurize until the system pressure reaches Kg/ ^cm2 ,
After reaching 18 Kg/cm ² , the system was stirred while releasing the pressure to 18 Kg/cm ² to start the polymerization reaction. During this time, the internal temperature rose slowly to 210°C, and after 5 hours, almost no water was distilled out, and at this point the internal temperature indicated 250°C. The pressure was further released, and after the system pressure was finally reduced to 700 mmHg, pressure was returned to the reactor, and the molten polymer was extracted from the bottom of the reaction tank. This polymer contains polyamide components from aliphatic diamines and isophthalic and terephthalic acids.
85% by weight and 15% by weight of lactam polyamide component
The polyamide resin had a relative viscosity ηrel of 2.0. This polyamide resin is designated as b-2. Examples 1 to 8, Comparative Examples 1 to 4 Polyamide (a) was 6/66 copolymerized nylon (80/20 Mitsubishi Kasei Novamid 2420).
After dry blending other ingredients shown in 1, 230
The fibers were melt-spun at a temperature of 8°C, solidified by cooling with cooling water at a water temperature of 8°C, and then stretched under the conditions shown in Table 1.
Stretched monofilaments each having a diameter of 2 mm were obtained. Table 1 also shows the transparency and Young's modulus of the obtained monofilament. The flexibility, wet nodule strength, and Young's modulus are values measured according to JIS L 1013. Note that the smaller the Young's modulus, the better the flexibility. Transparency is indicated by the haze value measured by arranging two monofilaments in a 3.8 mm slit and using a Tokyo Denshoku haze meter (TC-HDP). Therefore, the smaller the haze value, the better the transparency. The following bisamides were used. a: Ethylene bisstearamide b: Dioctadecyl terephthalic acid amide

[Table] Comparative Example 5 60 kg of ε-caprolactam and 300 ml of water were placed in a 200-inch autoclave, the temperature was raised to 150°C after the autoclave was sealed in an N ₃ atmosphere, and 7.5 kg of hexamethylene ammonium isophthalate and hexane terephthalate prepared separately were added. A 25% aqueous solution of 7.5 kg of methylene ammonium salt was pumped into 60 kg of ε-caprolactam using a chemotaxis pump. After feeding, the internal temperature was raised to 260°C while maintaining the internal pressure at 10 kg. After increasing the temperature, release the pressure.
A reduced pressure reaction was carried out at 150 torr for 2 hours. After introducing N ₃ and restoring the pressure to normal pressure, stop stirring and
The strands were extracted and pelletized, unreacted monomers were extracted and removed using boiling water, and the strands were dried. In this way, for 80 parts of caprolactam component (nylon 6 component), 10 parts of hexamethylene ammonium isophthalate component (6I component), and 10 parts of hexamethylene ammonium terephthalate component (6T component).
10 parts of copolyamide (6/6I/6T=80/
10/10). Moreover, ηrel was 3.8. After dry blending 0.25 parts by weight of ethylene bisstearamide and 10 parts by weight of ε-caprolactam to this raw material, polyamide monofilaments were produced under the same conditions as in Examples 1 to 8. The stretching conditions are as shown in Table-2. Table 2 shows various physical properties of the obtained monofilament. Comparative Example 6 The charged amount was 60 kg of ε-caprolactam, 1.58 kg of hexamethylene ammonium isophthalate, and 1.58 kg of hexamethylene ammonium terephthalate.
The same procedure as Comparative Example 5 was performed except that 6/
A copolyamide of 6I/6T=95/2.5/2.5 was obtained. The ηrel of this product was 3.8. A polyamide monofilament was produced in the same manner as in Comparative Example 5, and various physical properties were measured. The results are shown in Table-2. Comparative Example 7 Various physical properties were measured in the same manner as in Example 5, except that nylon 6 (ηrel=3.5) was used as the polyamide (a). The results are shown in Table-2.

〔Effect of the invention〕

As described above, according to the present invention, a polyamide monofilament having excellent transparency, flexibility, and knot strength can be obtained.

Claims (1)

[Claims] 1 (a) 100 parts by weight of nylon 6/66 copolymer (b) Polyamide containing aliphatic diamine and isophthalic acid and/or terephthalic acid as main components
0.5 to 20 parts by weight, plus total amount of polyamide (a) and (b) as required
A polyamide monofilament comprising a composition containing (c) 5 to 20 parts by weight of ε-caprolactam, and (d) 0.1 to 0.5 parts by weight of a bisamide represented by the following general formula [] and/or [], per 100 parts by weight. (In the formula, R ¹ is a divalent hydrocarbon group, R ² and R ³ are monovalent hydrocarbon groups, and R ⁴ and R ⁵ are hydrogen atoms or monovalent hydrocarbon groups.) 2 (a) Nylon 6/66 copolymer 100 parts by weight (b) Polyamide containing aliphatic diamine and isophthalic acid and/or terephthalic acid as main components
0.5 to 20 parts by weight, plus total amount of polyamide (a) and (b) as required
(c) ε-caprolactam 5 to 20 parts by weight (d) Bisamide represented by the following general formula [] and/or [] 0.1 to 0.5 parts by weight per 100 parts by weight (In the formula, R ¹ is a divalent hydrocarbon group, R ² and R ³ are monovalent hydrocarbon groups, and R ⁴ and R ⁵ are hydrogen atoms or monovalent hydrocarbon groups.) is extruded into a monofilament in a molten state, cooled and solidified with a cooling liquid below 25°C, then stretched 3.0 to 5.0 times at a temperature of 0°C to 100°C, and further stretched with heated air at 250 to 350°C. Stretched to 1.1 to 2.0 times in a 250 to 350°C heated air.
A method for producing polyamide monofilament characterized by annealing at a magnification of 1.0.