JP2716810B2 - Polyamide resin composition for filament and filament - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial application field) The present invention relates to a polyamide resin composition for filaments and filaments thereof, and more particularly to excellent strength and strength.
Resin compositions for mono- and multi-filaments having excellent elongation, excellent rigidity and pull-out force, excellent heat shrinkage / hot water shrinkage, and dimensional stability, and good texture for clothing, and mono and multi Regarding filament.

(Prior Art) Polyamide resins are widely used in monofilaments such as fishing lines, toothbrushes and magic fasteners, and multifilaments such as tire cords and clothing because of their excellent properties such as strength and elongation.

However, conventional polyamide resins have insufficient rigidity and elasticity in applications such as bristles (rough hair), magic fasteners, tire cords, carpets, and artificial turf used for some fishing lines, toothbrushes, and the like. A material having a high elastic modulus is desired. In addition, a stiff filament having a matte texture is desired for clothing.
Further, a material having a small shrinkage ratio when heated, such as during dyeing or ironing, and having stable dimensions is desired.

(Problems to be Solved by the Invention) The present invention improves the problems of filaments made of a conventional polyamide resin composition, has excellent strength and elongation,
Also, to provide a mono- and multi-filament resin composition and a mono- and multi-filament excellent in rigidity, pull-out force, heat shrinkage, hot water shrinkage, dimensional stability, and excellent feeling for clothing. Aim.

[Constitution of the Invention] (Means and Actions for Solving the Problems) The present invention relates to a polyamide resin (A) of 100 parts by weight and (A)
Layered silicate (B) uniformly dispersed in the components 0.05 to
30 parts by weight of a polyamide resin composition and a filament comprising the polyamide resin composition.

The polyamide resin (A) has an acid amide bond (-
CONH-), specifically, ε-caprolactam, 6-aminocaproic acid, ω-enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, Polymers or copolymers obtained from α-piperidone and the like; diamines such as hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and metaxylylenediamine, and terephthalic acid, isophthalic acid, adipic acid, and sebacic acid Examples of the polymer include a polymer or copolymer obtained by polycondensation with a dicarboxylic acid or a blend thereof.

The average molecular weight of the polyamide resin (A) is 10,000 to 30,0
00 is preferred.

If the average molecular weight is 10,000 or less,
Stretching is difficult, and if it exceeds 30,000, production of polyamide itself becomes difficult, which is not preferable.

The layered silicate (B) is a component for imparting rigidity, high elasticity, high pull-out force characteristics, and excellent feeling to the polyamide resin (A) without impairing its excellent tensile elongation characteristics.

When the layered silicate (B) is dispersed in the component (A),
It is preferable that the interlayer distance is maintained at an average of 20 ° or more on average and the layer is uniformly dispersed. Here, the interlayer distance refers to the distance between the centers of gravity of the plate of the layered silicate, and to uniformly disperse, the layered silicate is one by one, or a multilayer having an average overlap of 5 layers or less is parallel. Or, a state in which 50% by weight or more, preferably 70% by weight or more is dispersed without forming a local mass at random or in a state where parallel and random are mixed. Here, the layered silicate has a thickness of 6 to 20.
Å indicates a layered unit having a side of 0.002 to 1 μm.

As a raw material of such a layered silicate, a layered phyllo or a silicate mineral composed of a layer of magnesium silicate or aluminum silicate can be exemplified. In particular,
Examples include smectite-based clay minerals such as montmorillonite, saponite, beidellite, nontronite, hectorite, stevensite, vermiculite, halloysite, and the like, which may be natural or synthesized. You may. Of these, montmorillonite is preferred.

The composition of the component (A) and the component (B) is such that the component (B) is 0.05 to 30 parts by weight based on 100 parts by weight of the component (A).
If the composition of the component (B) is less than 0.05 parts by weight, the rigidity, elasticity, and pull-out force are not significantly improved, and if it exceeds 30 parts by weight, production becomes difficult, which is not preferable.

During the production of the composition or filament of the present invention, depending on the purpose, dyes, pigments, plasticizers, heat-resistant agents, clarifiers, lubricants,
An appropriate amount of an antistatic agent or the like can be appropriately compounded.

When the layered silicate (B) is a multilayered clay mineral,
(D) by contacting with a swelling agent of an amine such as octadecylamine or phenylenediamine, an amino acid such as 4-amino-n-butyric acid or 12-aminododecanoic acid or a lactam such as ε-caprolactam, And then mixing with a polyamide monomer and polymerizing (see JP-A-62-74957). Also, use a swelling agent and pre-
It is also possible to adopt a method in which the above is expanded and melt-kneaded with a polyamide resin or a resin containing the same to uniformly disperse them.

The filament of the present invention is obtained by melting the raw material composition in a melt extruder such as a single-screw extruder from a spinneret by a gear pump or the like for quantitatively controlling the discharge amount, and cooling with air or water. Meanwhile, it can be manufactured by taking at a predetermined take-up speed or the like.

Further, the obtained filament can be drawn at various magnifications depending on the application, and can be drawn simultaneously with the melt spinning.

The shape of the filament may be a single yarn, a plurality of yarns or a combination of a plurality of yarns, and the cross section thereof is not limited to a circle, and may be an irregular cross section such as a hollow or star shape.

(Effect of the Invention) The filament of the present invention can be used for various types of monofilaments and multifilaments. In particular, bristles for brushes, fishing lines, magic fasteners, tire cords, artificial turf, carpets, car seats, fishnets, ropes Gives products with high rigidity to applications such as yarn, filter, and yarn for filters. In addition, the shrinkage ratio when heated such as dyeing or ironing is small, and a product having a stable size and shape as a woven fabric is provided. Also, it can be used as a fiber for clothing having a strong and special texture.

(Example) Example 1 100 g of montmorillonite having an average thickness of one unit of the layered silicate of 9.5 mm and an average length of one side of about 0.1 μm is dispersed in 10 l of water, and 51.2 g of 12-amino acid is added thereto. 24m with dodecanoic acid
l of concentrated hydrochloric acid was added, and the mixture was stirred for 5 minutes and then passed. After sufficiently washing this, it was vacuum-dried. By this operation, ammonium 12-dodecanoate [NH ₃ ⁺ (CH ₂ ) ₁₁ COO
^- ] And montmorillonite were prepared. The layered silicate content in the composite was 80% by weight.

Next, 10 kg of ε-caprolactam, 1 kg of water and 90 g of the complex were placed in a reaction vessel equipped with a stirrer, and stirred at 100 ° C. so that the inside of the reaction system became uniform. The temperature was further raised to 260 ° C., and the mixture was stirred under a pressure of 15 kg / cm ² for 1 hour. Thereafter, the pressure was released, and the reaction was carried out at normal pressure for 2 hours while evaporating water from the reaction vessel. After completion of the reaction, the reaction product taken out in a strand form from the lower nozzle of the reaction vessel was water-cooled and cut to obtain a pellet comprising a polyamide resin (average molecular weight 15,000) and montmorillonite. The pellet was immersed in hot water to extract and remove unreacted monomer (about 10%), and then dried in vacuum to obtain a polyamide resin composition.

The materials thus obtained were subjected to the following evaluation tests.

(1) Monofilament evaluation test The test material was charged into an extruder under the following conditions, and the diameter was 1.47 mm.
It is melted and extruded from an 8-hole nozzle, cooled in 7 ° C. cooling water, pulled by the first roller, and further stretched at a take-up speed of the second roller 3.9 times that of the first roller (stretching temperature 250 ° C.). The take-up speed of the three rollers
5 times as large as the first roller and stretched further (stretching temperature 300
° C), and finally, the fourth roller was pulled at the same pulling speed as the third roller. During that time, the ambient temperature was set to 220 ° C, and heat-fixed to obtain a monofilament.

(Extruder conditions) Screw diameter: 30 mm Cylinder set temperature: C1 C2 C3 C4 N ° C 220 240 260 270 260 The following evaluation test was performed on the obtained monofilament.

1) Fineness 2) Tensile strength, elongation, and elastic modulus Measured according to JIS L1070, L1073 3) Pulling force When a jig shown in Fig. 1 is created and a filament is pulled out from a 10mm diameter hole with a hook-shaped jig Was measured with a load cell, and the maximum value was defined as the pull-out force.

4) Hot water shrinkage The sample is allowed to stand at 23 ° C. and a relative humidity of 65% until the weight becomes constant, and then cut into a length of 1,000 mm. This is immersed in water at 100 ° C. for 15 minutes, and the dimensions immediately after that are measured. Then, this hot water shrinkage is calculated in percentage.

(2) Multifilament evaluation test A sample was prepared using a spinning machine (screw diameter, manufactured by Shimadzu Corporation).
30mm, L / D = 23, compression ratio 3.5), Company's winding machine (STS-
1, a surface drive system, a single bobbin and a bobbin), and a spinning / drawing and twisting yarn was used to obtain a multifilament. The detailed conditions are as follows.

(Spinning conditions) 1) Set temperature of extruder: ° C C ₁ C ₂ C ₃ ADHD 210 230 250 260 260 250 2) Nozzle: 0.45mm diameter x 30 holes 3) Take-off speed: 700m / min 4) Filter: 40 / 40/75/125/250/325 mesh 5) Cooling air velocity: 0.6m / s 6) Oil agent: spinner F-160TS manufactured by Marubishi Yuka Co., Ltd. (Drawing and twisting conditions) 1) Drawing temperature: 170 ° C ( Hot pin) 2) Stretching ratio: 4 times 3) Stretching speed: 100 m / min As described above, a multifilament with a target of 240d / 30f was prepared.

The following evaluation test was performed on the obtained multifilament.

1) Fineness 2) Multifilament tensile elastic modulus Measured according to JIS L1070 and L1073.

3) The shine and flicker of the yarn were visually evaluated.

 The results are shown in the table.

Example 2 In Example 1, 10 kg of ε- was added to a reactor equipped with a stirrer.
The same experiment as in Example 1 was performed except that caprolactam, 1 kg of water and 180 g of a complex of ammonium 12-aminododecanoate and montmorillonite were added. The results are shown in the table.

Comparative Example 1 In Example 1, only 10 kg of ε-caprolactam and 1 kg of water were charged into a reactor equipped with a stirrer, and the same experiment as in Example 1 was performed without adding the complex. The results are shown in the table.

[Brief description of the drawings]

 FIG. 1 is an explanatory view of a jig for measuring a pull-out force.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akane Okada 41-1, Oku-cho, Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture Inside Toyota Central R & D Laboratories, Inc. (56) References JP-A-51-109998 (JP, A) JP-A-63-230766 (JP, A) JP-A-62-170515 (JP, A)

Claims (2)

(57) [Claims] 1. A polyamide resin composition for filaments comprising 100 parts by weight of a polyamide resin (A) and 0.05 to 30 parts by weight of a layered silicate (B). 2. A filament comprising the polyamide resin composition according to claim 1.