JP2001032132A - Polyamide resin filament - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin filament having excellent transparency and mechanical strengths. SOLUTION: The objective polyamide resin filament is composed of a polyamide resin containing ε-caprolactam as a principal constituent component and containing <=10.0 wt.% molecules having a molecular weight of 1,000-10,000 based on 100 wt.% of molecules having a molecular weight of >=1,000 in terms of polystyrene measured by gel permeation chromatography.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyamide resin filament containing ε-caprolactam as a main component, and more particularly, to a polyamide resin filament having excellent transparency and excellent mechanical strength.

[0002]

2. Description of the Related Art Conventionally, filaments of polyamide resin containing ε-caprolactam as a main component have excellent mechanical strength, toughness, abrasion resistance, chemical resistance and the like, and have remarkable elongation as fishing line, fish net, rope and the like. However, in terms of transparency, which is reduced by crystallization during molding, the market demand has not yet been sufficiently satisfied.

On the other hand, as a method of improving the transparency, a method of lowering the crystallinity by copolymerization is known. In this method, although the transparency is improved, at the same time, the elastic modulus and the like are lowered. This is particularly problematic in applications such as fishing nets where low tensile elongation is required. In addition, a method of adding a low molecular weight component such as fatty acid amide or caprolactam to a polyamide resin (see, for example, JP-A-1-85315). ) Is also known, but in this method, although the initial transparency is improved, the effect of improvement is not improved as intended due to bleed-out of these additives with the passage of time. At present, it is not possible to achieve both transparency and mechanical strength.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and accordingly, the present invention provides a polyamide resin filament having excellent transparency and excellent mechanical strength. The purpose is to:

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, the content of a low molecular weight substance having a specific molecular weight in a polyamide resin containing ε-caprolactam as a main component has been reduced. The present invention has been found to be important, that is, the present invention has ε-caprolactam as a main component, and has a molecular weight of 1,000 or more in terms of polystyrene measured by gel permeation chromatography. Is 100% by weight,
The content of molecules having a molecular weight of 1,000 to 10,000 is 1
A polyamide resin filament made of a polyamide resin having a content of 0.0% by weight or less is a gist of the invention.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamide resin according to the present invention is a polymer containing ε-caprolactam as a main component, and preferably has a content of ε-caprolactam of 70% by weight or more of all components, and is preferably 90% by weight. % Or more, more preferably 97% by weight or more.

Specific examples of these polyamide resins include homopolymers of ε-caprolactam, and other resins such as ε-caprolactam, butyrolactam, δ-valerolactam, enantholactam, ω-lauryl lactam and the like. Copolymer with lactams having 3 or more ring, ε-caprolactam, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecane Copolymers with amino acids such as acids, or ε-caprolactam, 1,4-butanediamine, 1,5-pentanediamine, 1,5-hexanediamine, 1,6-hexanediamine, 1,9- Nonanediamine, 1,11-undecadiamine, 1,12-dodecanediamine, α, ω-
Aliphatic diamines such as diaminopolypropylene glycol; alicyclic diamines such as 1,3- or 1,4-bis (aminomethyl) cyclohexane and bis (p-aminocyclohexylmethane); m- or p-xylylenediamine; Diamines such as aromatic diamines, and aromatic dicarboxylic acids such as glutaric acid, adipic acid, suberic acid, sebacic acid, and dodecane diacid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatics such as terephthalic acid and isophthalic acid And copolymers of dicarboxylic acids such as aromatic dicarboxylic acids. Among them, for example, homopolymers of ε-caprolactam (nylon 6) and copolymers of ε-caprolactam and ω-lauryl lactam (6 / 12 nylon), a copolymer of ε-caprolactam, 1,6-hexanediamine and adipic acid (6/6 Nylon), .epsilon. copolymers of caprolactam and 1,6-hexanediamine and terephthalic acid (6 / 6T nylon) and the like are preferable, and a homopolymer of .epsilon.-caprolactam (nylon 6) is preferred.

[0008] The polyamide resin in the present invention comprises:
Those having a molecular weight of 1,000 or more in terms of polystyrene measured by gel permeation chromatography
0% by weight, the molecular weight is from 1,000 to 10,000.
It is essential that the content of the molecule No. 00 is 10.0% by weight or less, the content is preferably 9.5% by weight or less, more preferably 9.0% by weight or less, and 8% by weight or less. .
It is particularly preferred that the content be 5% by weight or less. Molecular weight 1,0
If the content of the molecule of from 00 to 10,000 exceeds the above range, crystallization at the time of molding the polyamide resin is promoted, and the transparency as a filament is deteriorated.

Preferably, the polyamide resin has a hot water extraction rate of 2.0% by weight or less based on the total amount.

In the present invention, the polyamide resin is 185 ° C. by an isothermal crystallization method using a differential scanning calorimeter.
Is preferably 180 seconds or more, more preferably 220 seconds or more, and 250 seconds or more.
It is particularly preferred that the time is not less than seconds. Further, the recrystallization temperature after melting once is preferably 155 to 162 ° C, more preferably 156 to 162 ° C, and 157
It is particularly preferred that the temperature is １６161 ° C.

The polyamide resin of the present invention has a relative viscosity of 2.0-6.
It is preferably 5, more preferably 2.5 to 6.0, and particularly preferably 3.0 to 5.0.

[0012] Generally, a polyamide reaction product obtained by using ε-caprolactam as a main component contains unreacted monomers and its by-product oligomers. Extraction and removal of them as solubles by alcohol etc. are performed,
Thereby, those having a molecular weight of less than 1,000 are generally removed, but those having a molecular weight of not less than 10,000 and less than 10,000 are difficult to remove.

Accordingly, the polyamide resin in the present invention is preferably prepared by, for example, phosphoric acid, phosphorous acid, hypophosphorous acid, or a salt or ester thereof in melt polymerization generally performed using ε-caprolactam as a main component. In the presence of a phosphorus compound catalyst, 1.0% by weight of a polyaddition reaction accelerator such as a polyamide oligomer containing water, 6-aminocaproic acid and ε-caprolactam as main components in the initial stage of polymerization.
Above, the temperature is 220 ° C. or higher, preferably 250 ° C.
Above, more preferably at a high temperature of 260 ° C. or higher, and when the polyaddition reaction accelerator to be added is volatile such as water, the inside of the reactor is gauged at a gauge pressure of 0.2 MPa or more, preferably 0.3 MPa or more. Above, more preferably 0.5MP
a or more pressurized state, ring opening of ε-caprolactam,
It is preferably produced by accelerating a polyaddition reaction or the like.

The polyamide resin filament of the present invention is composed of the above polyamide resin, and the polyamide resin preferably contains a bisamide compound. ) Or (II) is preferred.

[0015]

Embedded image

[In the formulas (I) and (II), R ¹ is a divalent hydrocarbon group, R ² and R ³ are each independently a monovalent hydrocarbon group, R ⁴ and R ⁵ Each independently represents a hydrogen atom or a monovalent hydrocarbon group. ]

The bisamide compound represented by the formula (I) includes alkylamino diamines such as diaminomethane, diaminoethane, diaminopropane, diaminobutane, diaminohexane and diaminododecane, and arylenes such as phenylenediamine and naphthylenediamine. Diamines such as arylenedialkylenediamines such as diamines and xylylenediamine, and monocarboxylic acids such as hexanoic acid, octanoic acid, decanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, arachinic acid, behenic acid, and montanic acid Examples thereof include alkylenebisfatty acid amides, arylenebisfatty acid amides, arylenedialkylenebisfatty acid amides, and the like obtained by reaction with acids, among which N, N'-methylenebisstearic acid amide, N, N
N'-ethylenebisstearic acid amide is preferably used.

The bisamide compounds represented by the formula (II) include methylamine, ethylamine, butylamine,
Hexylamine, decylamine, octadecylamine,
Monoamines such as alkylamines such as dodecylamine, arylamines such as aniline and naphthylamine, aralkylamines such as benzylamine, cycloalkylamines such as cyclohexylamine, and adipic acid, sebacic acid, terephthalic acid, isophthalic acid, p-phenylene Examples thereof include those obtained by a reaction with a dicarboxylic acid such as range propionic acid, and among them, N, N'-dioctadecyl terephthalamide is suitably used.

In the present invention, the content of the bisamide compound is preferably from 0.05 to 0.5 parts by weight, based on 100 parts by weight of the polyamide resin.
More preferably, it is 1 to 0.3 parts by weight. When the content of the bisamide compound is less than the above range, the transparency as a filament tends to be inferior. On the other hand, when the content exceeds the above range, the mechanical strength tends to decrease and the appearance tends to be further impaired.

The polyamide resin according to the present invention may further include, in addition to the bisamide compound, a metal salt of an ethylene-acrylic acid copolymer in order to further improve the flexibility and knot strength of the filament. Resin or an elastomer component such as an ionomer resin such as an ion-modified ethylene resin, a polyamide-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, and an acrylic rubber may be contained. Stabilizers, antioxidants, light stabilizers, UV absorbers,
Antistatic agent, antiblocking agent, lubricant, release agent, plasticizer, thickener, crystallization accelerator, coloring agent, preservative, bactericide,
A drip-proof agent, a spreading agent, an impact resistance improving agent, and the like may be contained.

The polyamide-based resin filament of the present invention comprises the polyamide-based resin, the bisamide compound used as required, other resin, elastomer,
And other additives are dry-dried, melt-kneaded with a melt-kneading machine such as a single-screw or twin-screw extruder, and pelletized. After the method, or the above-mentioned other components are added and polymerized during the polymerization of the polyamide resin, the formed molding material is melt-extruded into a filament shape by an extruder by a method of pelletizing, and then cooled and solidified. Roll, oven, usually at a stretching temperature of about 80 to 250 ° C.
Known methods such as a dry stretching method by heating with infrared rays and dielectrics, and a wet stretching method by heating with hot water, an oil bath, etc.
At a stretch ratio of at least 4 times, preferably at least 4 times, more preferably at least 4.5 times, and stretched in one or more stages in the uniaxial direction.
It is manufactured by subjecting it to a heat setting treatment as required.

The polyamide resin filament of the present invention is excellent in transparency and mechanical strength. For example, it is suitably used as a monofilament for fishing lines, fish nets, ropes and the like, and as a textile filament for various fibers and the like.

[0023]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 60 kg of ε-caprolactam, 1.8 kg of water as a reaction accelerator, and 5 kg of disodium hydrogen phosphite as a catalyst
A 0.1% by weight aqueous solution was charged into a 200-liter autoclave, and after purging with nitrogen gas, the jacket was heated with stirring at 16 rpm while the autoclave was sealed, to reach an internal temperature of 270 ° C. and a gauge pressure of 0.7 MPa. At that point, release the pressure to atmospheric pressure, and then continue to 300 torr
The pressure was reduced to When the predetermined stirring power was reached, the stirring was stopped, the pressure was restored with nitrogen gas, the reaction product was extracted in the form of a strand, and pelletized with a rotary cutter, and the obtained pellet was purified using 150 liter of boiling pure water. The extraction operation is repeated five times to remove unreacted monomers and low molecular weight substances, and then at 120 ° C., 1 torr
And dried until the water content became 0.1% by weight or less.

With respect to the polyamide resin comprising the obtained ε-caprolactam homopolymer, the following method is used.
The content of molecules having a molecular weight of 1,000 to 10,000, and the rate of hot water extraction, and the half-crystallization time, recrystallization temperature,
The relative viscosity was measured, and the results are shown in Table 1.

A molecule having a molecular weight of 1,000 to 10,000
Of the treated polyamide resin sample was soluble in tetrahydrofuran and trifluoroacetylated in content trifluoroacetic acid, using gel permeation chromatography (manufactured by Tosoh Corporation "HLC-8020") manufactured by Tosoh Corp. as a column " TSKGEL G2000H ”,“ TS300
0H ”,“ G4000H ”and“ G5000H ”
Using a differential refractometer as a detector, using a tetrahydrofuran as an eluent, and obtaining a chart in terms of polystyrene from the elution time of a commercially available monodispersed standard polystyrene under the conditions of a flow rate of 1.0 ml / min, a molecular weight of 1, 000-1
The content (% by weight) of the 000 molecule was determined by cutting out the chart and weighing it.

Hot water extraction rate After extracting a polyamide resin sample in accordance with JIS K6810, a total organic carbon analyzer ("TO" manufactured by Shimadzu Corporation)
TAL ORGANIC CARBON ANALYZ
ER TOC-500 ").

Semi-crystallization time 5 ± 0.5 mg of a polyamide resin sample was weighed into an aluminum pan, and was measured by a differential scanning calorimeter (“D” manufactured by PerkinElmer).
SC2 ”) in a nitrogen atmosphere from room temperature to 20 ° C /
The temperature was raised to 260 ° C. at a rate of 1 minute, the temperature was maintained for 3 minutes, and then the temperature was lowered to 185 ° C. at a rate of 100 ° C./min or more. ) Was measured.

Recrystallization temperature 5 ± 0.5 mg of a polyamide resin sample was weighed into an aluminum pan, and a differential scanning calorimeter (“SS” manufactured by Seiko Denshi Co., Ltd.) was used.
C5000 ") in a nitrogen atmosphere from room temperature to 20
The temperature was raised to 260 ° C. at a rate of ° C./min, and the temperature was maintained for 3 minutes. Then, the temperature was lowered to 80 ° C. at a rate of 20 ° C./min. It was measured.

Relative viscosity Measured in 98% sulfuric acid according to JIS K6810.

Next, the obtained polyamide resin 100
Parts by weight, dry blending of 0.2 parts by weight of N, N'-ethylenebisstearic acid amide as a bisamide compound and 0.1 parts by weight of n-butylbenzenesulfonamide as a spreading agent. Is melt-extruded at 260 ° C. from a single screw extruder having a cylinder diameter of 30 mm and L / D27, and is spun through a cooling water at 10 ° C. to be cooled and solidified.
Under H, the film is stretched 3.8 times in hot air, further stretched 1.3 times in dry air at 240 ° C.,
A monofilament having a diameter of 1.0 mm was formed by performing dry heat fixing at a relaxation rate of 0.95 times in dry air at 0 ° C.

With respect to the obtained monofilament, transparency and mechanical strength were measured by the following methods, and the results are shown in Table 1.

Transparency The light transmittance (dBm) in the length direction of the monofilament cut to a length of 300 mm was measured using an OptiPower meter (manufactured by Soar). In addition, as for the light transmittance, the closer to 0, the better the transparency.

Mechanical Strength Tensile strength (gf / D) per denier (D) was measured according to JIS L1013.

Example 2 In Example 1, the amount of water used as the reaction accelerator was set to 0.6 kg, and the internal temperature of the autoclave was set to 240 kg.
C. and a gauge pressure of 0.3 MPa, except that a polyamide resin was obtained in the same manner as in Example 1 and the obtained polyamide resin had a molecular weight of 1,000 to 10,000.
The content of molecules of 00 and the hot water extraction rate, as well as the half-crystallization time, recrystallization temperature, and relative viscosity were measured, and further, a monofilament was molded. The strength was measured, and the results are shown in Table 1.

Comparative Example 1 A 200 liter autoclave was charged with 60 kg of ε-caprolactam, 0.24 kg of water as a reaction accelerator, and 0.1 liter of a 5% by weight aqueous solution of sodium phosphite as a catalyst. The jacket was heated while stirring at 16 rpm while the autoclave was sealed, and when the internal temperature reached 150 ° C. and the gauge pressure reached 0.1 MPa, the internal temperature was further increased while releasing the pressure so as to maintain 0.1 MPa. When the temperature reached 210 ° C., the pressure was released to atmospheric pressure, and subsequently reduced to 300 torr. When the predetermined stirring power was reached, the stirring was stopped, the pressure was restored with nitrogen gas, the reaction product was extracted in the form of a strand, and pelletized with a rotary cutter.
Unreacted monomers and low molecular weight substances were removed by repeating the extraction operation using 0 liter of boiling pure water five times, and then the water content was reduced to 0.1 at 120 ° C. and 1 torr.
It was dried until it was less than% by weight.

In the same manner as in Example 1, the obtained polyamide resin had a molecular weight of 1,000 to 10,000.
The content of the molecule, and the hot water extraction rate, and the half-crystallization time, recrystallization temperature, and relative viscosity were measured. Further, a monofilament was formed, and the obtained monofilament was evaluated for transparency and mechanical strength. Was measured, and the results are shown in Table 1.

[0038]

[Table 1]

[0039]

According to the present invention, it is possible to provide a polyamide resin filament having excellent transparency and excellent mechanical strength.

Continued on front page F-term (reference) 4J001 DA01 DB01 DB04 EA02 EA06 EA12 EA15 EB03 EB08 EB09 EB14 EB36 EB37 EC03 EC14 EC47 EC48 EE53E HA02 JA01 JA10 JB01 JB21 JB42 4L035 BB31 BB91 DD14 EE07 EE08 JJ02FF

Claims (2)

[Claims] (1) ε-caprolactam as a main component,
Those having a molecular weight of 1,000 or more in terms of polystyrene measured by gel permeation chromatography
0% by weight, the molecular weight is from 1,000 to 10,000.
A polyamide-based resin filament comprising a polyamide-based resin having a content of molecules of No. 00 of 10.0% by weight or less. 2. The polyamide resin filament according to claim 1, wherein the polyamide resin contains 0.05 to 0.5 parts by weight of a bisamide compound based on 100 parts by weight of the resin.