KR100596092B1 - Polyamid monofilament - Google Patents

Abstract

The present invention provides a single filament that can obtain a stable commodity value by improving the problem of surface layer detachment during use, which occurs in a large single filament containing a plasticizer or the like.

(a) 100 parts by weight of polyamide resin having 6 nylon units as its main structural unit,

(b) 1 to 20 parts by weight of ε-caprolactam and

(c) a polyamide single having a diameter of 0.4 to 10 mm, containing 0.3 to 20 parts by weight of an ester compound of p-hydroxybenzoic acid and / or o-hydroxybenzoic acid with a C12-22 aliphatic alcohol having a side chain. filament.

Description

Polyamide Single Filament {POLYAMID MONOFILAMENT}

The present invention relates to polyamide single filaments. Specifically, the present invention relates to a long-lasting fishing tex (stem line and branch line) made of a single filament made of polyamide resin having high strength, excellent flexibility, and excellent properties such that defects such as surface layer peeling do not occur when used.

Single filaments made of polyamide resin are widely used in fishing longlines, fishing nets and leisure fishing lines because of their high strength, flexibility and transparency.

In particular, single filament for large diameter fishing line (hereinafter referred to as large single filament) used for long-line fishing, etc. is the biggest problem not only in strength but also in flexibility reduction due to large diameter and poor handling in operation. Has been. In addition, good transparency may be necessary in order to improve the merchandise value.

Large single filaments satisfying the above requirements are formulated with a typical ε-caprolactam as a plasticizer for imparting flexibility, and an aromatic polyamide or bisamide compound mainly composed of aliphatic diamine, isophthalic acid and / or terephthalic acid for imparting transparency. Compounding (for example, Japanese Patent Publication No. 1-8531) has been performed.

However, a large single filament containing ε-caprolactam has a problem of deterioration of the surface value due to peeling at the surface layer during operation or storage in the ship or storage (exposed to high temperature and high humidity), thereby deteriorating the product value.

In order to solve the above-mentioned problems, a proposal (Japanese Patent Publication No. 8-269817) to optimize the continuously changing crystal structure from the center of a single filament to the surface layer portion has been proposed. However, this proposal is insufficient to improve the peeling phenomenon of the single filament surface layer portion and could not be completely suppressed.

SUMMARY OF THE INVENTION An object of the present invention is to provide a single filament which can obtain stable product value by improving the surface layer peeling problem in use occurring in a large single filament containing a plasticizer or the like as described above.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, as a result of earnest examination, the present inventors discovered that the single filament made from polyamide resin which mix | blended certain specific additives did not generate surface layer peeling at the time of use, and completed this invention.

That is, the gist of the present invention

(a) 100 parts by weight of polyamide resin having 6 nylon units as its main structural unit,

(b) 1 to 20 parts by weight of ε-caprolactam and

(c) a polyamide single having a diameter of 0.4 to 10 mm, containing 0.3 to 20 parts by weight of an ester compound of p-hydroxybenzoic acid and / or o-hydroxybenzoic acid with a C12-22 aliphatic alcohol having a side chain. Filament.

Hereinafter, the present invention will be described in detail.

In the present invention, the polyamide resin used as the component (a) is composed of 6 units of nylon (pentamethyleneamide units) in which the ε-caprolactam is ring-opened and polymerized, that is, a homopolymer having at least 50% by weight of 6 units of nylon. Or copolymers. Other structural units that are copolymerized components include three-membered or more lactams, polymerizable ω-amino acids, polyamide structural units introduced by dibasic acids and diamines, and the like. Specifically, ω-amino acids or phthalic acids, adips such as lactams such as α-pyrrolidone, α-piperidone, enanthlactam, capryllactam, lauryllactam, 7-aminoheptanoic acid, and 11-aminoundecanoic acid Polyamide constituent units introduced by dibasic acids such as acid, sebacic acid, dodecanoic acid, terephthalic acid, isophthalic acid, and diamines such as hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and methoxyxylenediamine Can be mentioned.

Polyamide resins composed of these structural units include polyamide 6, 6/66 (formed from adipic acid and hexamethylenediamine), 6/12 (obtained by ring-opening polymerization of ω-laurolactam), 6 / 6T ( Formed from terephthalic acid and hexamethylenediamine), 6/66 / 6T, and the like. The polyamide resin is selected according to the application, but particularly, a large single filament is preferably a copolymer having 6 nylon units such as polyamide 6/66, 6/12 and 6 / 6T as the main structural unit.

As for the molecular weight of polyamide resin, the relative viscosity measured by JIS-K-6810 is 2.5-5.5, Preferably the thing of 3.0-5.0 is used.

In the present invention, the ε-caprolactam used as the component (b) is 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the polyamide resin containing 6 units of nylon (a) as the main structural unit. It is preferable to mix | blend in a negative ratio. When the compounding quantity of (epsilon) -caprolactam is less than 1 weight part, there is no flexibility improvement effect, and when a compounding quantity exceeds 10 weight part, a dough defect will arise and a stable spinning cannot be performed.

On the other hand, [epsilon] -caprolactam is a monomer of polyamide 6, and in polyamide 6 immediately after polymerization, a considerable amount remains as unreacted monomer, which is usually subjected to extraction to melt spinning at 0.5 wt% or less. Therefore, when there is much residual amount in the polyamide resin used by this invention, it is good to make it the total amount of the epsilon caprolactam which remain | survives and the epsilon caprolactam added add to the said compounding quantity range.

The ester compound used as component (c) of the present invention is an ester compound of p-hydroxybenzoic acid and / or o-hydroxybenzoic acid with a C12-C22 aliphatic alcohol having a side chain. When the carbon number of the aliphatic alcohol is less than 12, the thermal stability of the ester compound is lowered, and it decomposes and scatters during melt spinning. On the other hand, when carbon number of an aliphatic alcohol exceeds 22, compatibility with polyamide resin will fall and transparency and intensity | strength of a single filament will fall. In addition, compatibility with the polyamide is lowered when the aliphatic alcohol does not have a side chain.

The compounding quantity of the said ester compound used in this invention is 0.3-20 weight part, Preferably it is 0.5-10 weight part with respect to 100 weight part of polyamide resin which has 6 nylon units which are (a) component as a main structural unit. If the amount is less than 0.3 part by weight, the effect of suppressing peeling or whitening is not exerted when using a single filament. If the blending amount is more than 20 parts by weight, the strength of the single filament is lowered.

When good transparency is required for the single filament of the present invention, it is preferable to mix | blend the aromatic polyamide which is (d) component.

The aromatic polyamide used as the component (d) is a fiber-formable polyamide mainly composed of aliphatic diamine and isophthalic acid and / or terephthalic acid. Specifically, the homopolymer or copolymer composed of aliphatic diamine and terephthalic acid and / or isophthalic acid is a main component, and preferably the homopolymer or copolymer composed of 85% by weight or more of aliphatic diamine and terephthalic acid and / or isophthalic acid.

Terephthalic acid and isophthalic acid, which are the main components of the aromatic polyamide, are used in any ratio, but are preferably terephthalic acid / isophthalic acid = 10/90 to 50/50 (weight ratio). Aliphatic diamines which are the main components of the aromatic polyamide include ethylenediamine, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine and the like, and methylene groups of these compounds include methylated, ethylated or halogenated derivatives. In 1 type, or 2 or more types can be used.

The aromatic polyamide may be a polymer having a main component of 100% by weight, but a three-membered or more lactam or polymerizable ω- used in a polyamide resin having the main component of 85% by weight or more as another component, for example, the nylon 6 unit as the main structural unit. The copolymer which consists of components, such as a polyamide structural unit introduce | transduced by amino acid, a dibasic acid, and diamine, and 15 weight% or less may be sufficient.

Specifically, among the components which can be used in the case of a copolymer, caprolactam, lauryl lactam, etc. are mentioned. Examples of the diamine include 2,2-bis (4-amino-3-methylcyclohexyl) propane, methoxyxylenediamine, isophoronediamine, and the like in addition to the aliphatic diamines exemplified as the main component of the aromatic polyamide. Examples of the carboxylic acid include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and derivatives in which the methylene group of the compound is methylated, ethylated or halogenated. have. In the superposition | polymerization of a main component polymer manufacture, a copolymer can be obtained by using together 1 type (s) or 2 or more types in the form of the polyamide formation component which consists of the said diamine and dicarboxylic acid.

In the present invention, the aromatic polyamide compounding amount that can be used is preferably 5 to 20 parts by weight, more preferably 1 to 1 with respect to 100 parts by weight of the polyamide resin having 6 nylon units as the main component (a). 15 parts by weight. When the compounding amount is less than 0.5 part by weight, there is no transparency improving effect, and when the compounding amount exceeds 20 parts by weight, the flexibility is inferior.

The molecular weight of the aromatic polyamide is 280 ℃, is a melt viscosity measured at a shear rate of 100 s ^-l is used it is usually 2000 to 10000 poise, preferably from 3500 to 7500 poise.

In the present invention, the bisamide compound used as the component (e) is a compound represented by the following general formula (1) or (2).

Wherein R ¹ is a divalent hydrocarbon group, R ² and R ³ are monovalent hydrocarbon groups, R ⁴ and R ⁵ represent a hydrogen atom or a monovalent hydrocarbon group, and R ² and R ³ and R ⁴ and R ⁵ May be the same or different, respectively.

Bisamide compounds represented by the formula (1) include alkylenediamines such as methylenediamine, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, octamethylenediamine, and dodecamethylenediamine; Diamines such as arylenedialkylamines such as xyleneylene diamine, stearic acid, hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, arachidic acid, behenic acid, oleic acid, erydinic acid, All alkylene bis fatty acid amides, alkylene bis fatty acid amides and arylene dialkylene bis fatty acid amides obtained by reaction with fatty acids such as montanic acid are included, but representative examples are N, N'-methylene bis stearic acid amide, N And N'-ethylenebisstearic acid amide.

In addition, the bisamide compound represented by the formula (2) may be an alkylamine such as ethylamine, methylamine, butylamine, hexylamine, decylamine, pentadecylamine, octadecylamine, dodecylamine; Arylamines such as aniline and naphthylamine; Aralkyl amines such as benzyl amine; Monoamines, such as cycloalkylamines, such as cyclohexylamine, and all those obtained by the reaction of dicarboxylic acids, such as terephthalic acid, p-phenylenedipropionic acid, succinic acid, and adipic acid, are included, but typical examples are N, N'- And dioctadecyl dibasic acid amides such as dioctadecyl terephthalic acid amide.

These bisamide compounds are used alone or as a mixture without distinguishing whether they are compounds represented by any of the two formulas.

In this invention, the compounding quantity of the bisamide compound to be used becomes like this. Preferably it is 0.1-0.5 weight part, More preferably, it is 0.15 thru | or 100 weight part with respect to 100 weight part of polyamide resin which has 6 units of nylon (a) components as a main structural unit. 0.4 parts by weight. If the blending amount is less than 0.1 part by weight, the single filament surface is whitened. If the blending amount is more than 0.5 part by weight, defects such as breaking of the yarn during melt spinning occur.

In this invention, the method of mix | blending each component is performed by arbitrary methods until just before melt spinning.

For example, a method of mixing each component in a blender (dry mixing method), a method of mixing each component by using a single screw or twin screw extruder to obtain a pallet composed of each component (compound method), (b) to (e) Component (a) is mixed with polyamide resin containing 6 units of nylon (a) as the main constituent unit during melt spinning when the master batch put into the (a) component is preliminarily beaten using a single or twin screw extruder. And dilution, followed by molding (master batch method).

In addition, the polyamide resin composition containing the components (a) to (c) and / or (c) and (d) is a lubricant, a release agent, and a thermal deterioration inhibitor separately from the compound within a range not impairing the properties as a single filament. And additives such as ultraviolet absorbers, antistatic agents, dyes, and pigments.

The polyamide single filaments of the invention can be melt spun with conventional single filament spinning devices. For example, as shown in Japanese Patent Application Laid-Open No. 63-235524 or Japanese Patent Publication No. Hei 1-853l, after extruding with an extruder, it is immersed in water or solidified by air cooling to obtain wet or dry multistage stretching and heat setting. Can be.

Since the polyamide single filament of the present invention is a long fishing tex (stem line and branch line), if too thin, the tensile strength is insufficient and is not suitable for the long line fishing. In addition, if the filament is too large, the tensile strength is sufficient, but the string is hardened and the handleability is poor, which is not suitable for the longline fishing. Therefore, the polyamide single filament diameter of the present invention is 0.4 to 10 mm, preferably 0.5 to 9 mm, more preferably 0.6 to 8 mm.

Example

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to a following example, unless the summary is exceeded.

In addition, the obtained single filament was evaluated in the following procedures.

(A) Peelability evaluation

After the single filament was allowed to stand for 20 hours at 80 ° C. and 95% RH, the presence or absence of peeling was visually evaluated.

(B) flexibility

Young's modulus was measured based on JIS-L-1013. The lower the Young's modulus, the better the flexibility.

(C) transparency

15 single filaments cut to a length of 120 mm were placed side by side in a raft, and total light transmittance was measured by a haze meter manufactured by Tokyo Electric Color Co., Ltd. Transparency is better when the total light transmittance is close to 100%.

Reference Example 1 (Preparation of Polyamide Resin 6/66 Copolymer with 6 Units of Nylon as Main Constituent Unit)

The 50% aqueous solution of the epsilon caprolactam and the salt of adipic acid and hexamethylenediamine (hereinafter abbreviated as "AH salt") was heated to 100 ° C, respectively.The weight ratio of epsilon caprolactam and AH salt was 82/18. After mixing so that the mixture was put into a 200 liter reactor with a stirrer, the temperature was increased from 13 kg / cm ² to 270 ° C., and then the pressure was gradually reduced to 0.5 kg / cm ² while maintaining the internal temperature at 245 ° C., whereby the stirring power was a predetermined value. When it came to a stop immediately.

Then, nitrogen was introduced to recover the pressure, and the molten polymer was extracted from the reactor bottom, pelletized, extracted with boiling water, and dried.

As for the unreacted epsilon caprolactam of this polymer, 0.5 weight% and relative viscosity were 4.6 when it measured based on JIS-K-6810.

Reference Example 2 (Aromatic Polyamide Preparation)

2.28kg hexamethylenediamine 90% aqueous solution

9.0 kg of water

1.96kg of isophthalic acid

Terephthalic Acid 0.98kg

And 11.0g of acetic acid was added to an aqueous solution comprising salt into the reaction vessel equipped with a stirrer was sufficiently replaced with nitrogen, the inside pressure is raised heated until 18kg / cm ² The pressure in the system was stirred while maintaining the bangap 18kg / cm ² . At this time, the internal temperature was gradually increased at 210 ℃ and after 5 hours almost no water outflow and the internal temperature at this point was 250 ℃. After further depressurizing and finally reducing the pressure in the system to 700 mmHg, the pressure was restored and the molten polymer was removed from the reactor bottom and pelletized.

The polymer has a melt viscosity was measured in the aliphatic diamine and isophthalic acid and a polyamide-forming component composed of terephthalic acid is 280 ℃ to the aromatic polyamide 100% by weight, and a shear rate of 100s ^-l 4000 poise.

Reference Example 3 (Preparation of p-hydroxybenzoic acid ester)

p-hydroxybenzoic acid and 2-hexyldecanol (16 carbon atoms) were dehydrated by heating at 200 to 260 ° C. to obtain 2-hexyldecanol ester of p-hydroxybenzoic acid.

Preparation of Polyamide Resin Compositions 1 to 6 (Pallets)

The polyamide resins obtained in Reference Examples 1 and 2 and the ester compound obtained in Reference Examples 3 were optionally blended with the ε-caprolactam and bisamide compounds in the ratios shown in Table 1, and then biaxially attached with a vent with a cylinder particle diameter of 30 mm. Pellets were melted and kneaded at a cylinder temperature of 240 ° C. using an extruder (EXT. TEX30) to obtain a polyamide resin composition pallet. Subsequently, drying of the obtained pallet was carried out at a temperature of 120 ° C. using a vacuum dryer, and the internal pressure was set at a reduced pressure of 760 mmHg as a gauge of a bourdon tube installed in the apparatus for 6 hours.

Table 1

Examples 1-6

The specific polyamide resin composition shown in Table 1, the epsilon caprolactam, and the bisamide compound were dry-mixed with a tumble blender at the compounding ratio shown in Table 2, respectively.

The mixture was melt-spun with an extruder equipped with a gear pump at the end of a single screw extruder equipped with a full flight screw of 40 mm in cylinder diameter and L / D = 27, and passed through a cooling water tank having a water temperature of 15 ° C. to solidify cooling. After carrying out the wet heat stretching at 3.2 times under 95 ° C. and 100% RH, dry heat stretching was carried out at 1.5 times in dry air at 280 ° C., followed by dry heat annealing with a relaxation rate of 0.95 times at 290 ° C. or lower to obtain a single filament having a diameter of 3 mm.

The obtained single filament was evaluated for transparency, Young's modulus and peelability. The results are shown in Table 2.

Example 7

The polyamide resin composition shown in Table 1 was melt-spun with an extruder equipped with a gear pump at the end of a single screw extruder equipped with a full-flight screw with a cylinder particle diameter of 40 mm and L / D = 27, and passed through a cooling water tank having a water temperature of 15 ° C. to cool. After solidification, wet heat stretching is performed 3.2 times below 95 ° C. and 100% RH, followed by dry heat stretching 1.5 times in dry air at 280 ° C., and finally dry heat annealing at 0.95 times relaxation rate below 290 ° C. to form a single filament with a diameter of 3 mm. Thus, the transparency, Young's modulus, and peelability were evaluated as in Examples 1 to 6, and the results are shown in Table 2.

Comparative Examples 1 to 4

The polyamide 6/66 copolymer prepared in Reference Example 1, the aromatic polyamide prepared in Reference Example 2, ε-caprolactam and bisamide were dry mixed with a tumbler blender at the compounding ratios shown in Table 2.

Thereafter, a single filament having a diameter of 3 mm was obtained in the same manner as in Examples 1 to 6, and transparency, Young's modulus, and peelability were evaluated. The results are shown in Table 2.

Comparative Examples 5-7

The polyamide resin composition of Table 1 and the aromatic polyamide, ε-caprolactam and bisamide compound prepared in Reference Example 2 were dry mixed with a tumbler blender at the compounding ratios shown in Table 2.

Thereafter, a single filament having a diameter of 3 mm was obtained in the same manner as in Examples 1 to 6, and transparency, Young's modulus, and peelability were evaluated. The results are shown in Table 2.

TABLE 2

Note: 1. The types of polyamide resin compositions are shown in Table 1.

    2. The actual bisamide compound used is N, N'-ethylenebisstearic acid amide.

According to the present invention, it is possible to obtain a single filament in which surface peeling does not occur during use (when fishing in a fish tank, in storage on a boat or in a warehouse).

Claims (5)

(a) l00 parts by weight of polyamide resin having 6 nylon units as its main structural unit, (b) 1 to 20 parts by weight of ε-caprolactam and (c) a polyamide single having a diameter of 0.4 to 10 mm, containing 0.3 to 20 parts by weight of an ester compound of p-hydroxybenzoic acid and / or o-hydroxybenzoic acid with a C12-22 aliphatic alcohol having a side chain. filament. The polyamide single filament according to claim 1, further comprising 0.5 to 20 parts by weight of an aromatic polyamide (d) which is composed mainly of aliphatic diamine and isophthalic acid and / or terephthalic acid. The polyamide single filament according to claim 1 or 2, further comprising 0.1 to 0.5 parts by weight of the bisamide compound represented by the following general formula (1) and / or the bisamide compound represented by the general formula (2). .

(One)

(2) Wherein R ¹ is a divalent hydrocarbon group, R ² and R ³ are monovalent hydrocarbon groups, R ⁴ and R ⁵ represent a hydrogen atom or a monovalent hydrocarbon group, and R ² and R ³ and R ⁴ and R ⁵ May be the same or different, respectively. Longline fishing tex consisting of a polyamide single filament according to claim 1. Longitudinal fishing tex consisting of the polyamide single filament according to claim 3.