JPH0381364A - Polyamide resin composition for filament and filament made therefrom - Google Patents

Abstract

PURPOSE:To provide a polyamide resin composition which yields mono and multifilaments excellent in strength, elongation, rigidity, drawability, thermal shrinkage, dimensional stability, etc., by compounding a polyamide resin with a specified amount of a layered silicate. CONSTITUTION:The title composition comprises 100 pts.wt. polyamide resin, e.g. nylon 6, and 0.05-30 pts.wt. layered silicate, e.g. montmorillonite. When a multilayered clayey mineral is used as the silicate, this composition can be prepared by bringing the silicate into contact with a swelling agent, such as octadecylamine, 12-aminododecanoic acid or epsilon-caprolactam, to widen the gap between the layers themselves to thereby facilitate the incorporation of polyamide monomers, mixing the resultant silicate with the monomers, and polymerizing the monomers. Filaments produced by spinning the obtained composition are suitably used in producing fishlines, ropes, fibers for apparel use, etc.

Description

Detailed Description of the Invention [Objective of the Invention] (Industrial Field of Application) The present invention relates to a polyamide resin composition for filaments and filaments thereof, and more specifically, the present invention relates to a polyamide resin composition for filaments and filaments thereof, and more specifically, has excellent strength and elongation, and has high rigidity and Excellent pulling force and heat shrinkable
The present invention relates to resin compositions for mono- and multifilaments and mono- and multifilaments that have excellent hot water shrinkability and dimensional stability and have a good feel for clothing.

(Prior Art) Due to its excellent properties such as strength and elongation, polyamide resin is widely used for monofilaments such as fishing lines, toothbrushes, and magic fasteners, and for multifilaments such as tire cords and clothing.

However, conventional polyamide resins do not have sufficient rigidity and elastic modulus for applications such as fishing lines, bristles used in toothbrushes, magic fasteners, tire cords, carpets, and artificial turf. Materials with high elastic modulus are desired. In addition, for clothing, rigid filaments with a matte texture are desired. In addition, a material that has a small shrinkage rate when heated during dyeing, ironing, etc., and has stable dimensions is desired.

(Problems to be Solved by the Invention) The present invention improves the problems of filaments made of conventional polyamide resin compositions, and provides excellent strength and elongation, as well as rigidity, pull-out force, heat shrinkage, and heat shrinkage. The object of the present invention is to provide a resin composition for mono- and multi-filaments, and mono- and multi-filaments, which have excellent water shrinkage properties and dimensional stability, and have an excellent feel for clothing.

[Structure of the Invention] (Means and Effects for Solving the Problems) The present invention comprises 100 parts by weight of a polyamide resin (A) and 0.05 parts of a layered silicate (B) uniformly dispersed in component (A). ~30 parts by weight of a polyamide resin composition and a filament made of the polyamide resin composition.

Polyamide resin (A) has an acid amide bond (-C
ONH-), specifically ε-caprolactam, 6-aminocaproic acid, ω-enantholactam, 7-aminohbutanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone. , α-piperidone, etc.: diamines such as hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, metaxylylene diamine, and terephthalic acid, isophthalic acid, adipic acid, and sepacin. Examples include polymers or copolymers obtained by polycondensation with dicarboxylic acids such as acids, or blends thereof.

The average molecular weight of the polyamide resin (A) is 10.000~
30.000 is preferred.

If the average molecular weight is less than 10,000, it will be difficult to spin and draw filaments, and if it is more than 30,000, it will be difficult to produce the polyamide itself, which is not preferred.

The layered silicate (B) imparts rigidity, high elasticity, and
It is a component for imparting high pull-out force characteristics and excellent texture.

When dispersed in component (A), layered silicate (B) preferably maintains an average glabellar distance of 20 Å or more and is uniformly dispersed. Here, the distance between the eyebrows refers to the distance between the centers of gravity of the flat plates of layered silicate, and uniform distribution means that each sheet of layered silicate is distributed in parallel, or a multilayered material with an average overlap of 5 or less layers is distributed in parallel. Or, it refers to a state in which 50% by weight or more, preferably 70% by weight or more, is dispersed randomly or in a mixed state of parallel and random without forming local lumps.Here, the layered silicate is , indicates a layered unit with a thickness of 6 to 20 mm and a side of 0.002 to IP.

As a raw material for such a layered silicate, a layered phyllosilicate mineral composed of a layer of magnesium silicate or aluminum silicate can be exemplified. Specifically, examples include smectite clay minerals such as montmorillonite, sabonite, beidellite, nontronite, hectorite, and stevensite, as well as vermiculite and halloysite, which may be natural or synthetic. It may be something that has been done. Among these, montmorillonite is preferred.

The composition of component (A) and component (B) is such that component (B) is present in an amount of 0.05 to 30 parts by weight per 100 parts by weight of IfJ (A). If the composition of component (B) is less than 0.05 parts by weight, the improvement in rigidity, elasticity, and pull-out force will not be significant;
If it exceeds 0 parts by weight, production becomes difficult, which is not preferable.

When producing the composition or filament of the present invention, appropriate amounts of dyes, pigments, plasticizers, heat resistant agents, clarifying agents, lubricants, antistatic agents, etc. may be blended depending on the purpose.

When the layered silicate (B) is a layered clay mineral, (
di) Contact with a swelling agent such as an amine such as octadecylamine or phenylene diamine, an amino acid such as 4-amino-n-butyric acid or 12-aminododecanoic acid, or a lactam such as ε-caprolactam to prepare the area between the eyebrows beforehand. A method of spreading the monomer between the eyebrows to make it easier to take it in, then mixing it with a polyamide monomer and polymerizing it (Japanese Patent Application Laid-Open No. 62-74957)
Alternatively, a swelling agent may be used to expand the glabella to 20 angstroms or more in advance, and the mixture may be melted and mixed with a polyamide resin or a resin containing the same to uniformly disperse it.

The filament of the present invention is produced by melting the raw material composition using a single-screw melt extruder, extruding it from a spinneret using a gear pump or the like that quantitatively controls the discharge amount, and cooling it with air or water. However, it can be manufactured by taking it at a predetermined take-up speed.

Furthermore, the obtained filaments can be drawn at various magnifications depending on the use, and can be drawn simultaneously during the above-mentioned melt spinning.

The shape of the filament may be a single thread, multiple threads, or multiple threads twisted together, and its cross section is not limited to a circular shape, but may have an irregular cross section such as a hollow or star shape.

(Effects of the Invention) The filament of the present invention can be used for various monofilaments and multifilaments, particularly bristles for brushes, fishing lines, magic fastener tire cords, artificial turf,
It provides highly rigid products for uses such as carpet, car seats, fishing nets, ropes, ropes, and filter threads. In addition, it has a small shrinkage rate when heated during dyeing, ironing, etc., and provides a product with stable dimensions and shape as a textile. It can also be used as a fiber for clothing with a special stiff texture.

(Example) Example 1 The average thickness of one unit of layered silicate is 9.5 mm, and the average length of one side is approximately 0.5 mm. IP montmorillonite 100g 1
042 was dispersed in water, 51.2 g of 12-aminododecanoic acid and 24-chloride concentrated hydrochloric acid were added thereto, stirred for 5 minutes, and then clarified. Furthermore, after thoroughly washing this, it was vacuum dried. Through this operation, a composite of ammonium 12-dodecanoate [NHs'' (cHil I + coo-) and montmorillonite was prepared. The layered silicate content in the composite was 80% by weight.

Next, 10 kg of ε-prolactam, 1 kg of water, and 90 g of the above complex were placed in a reaction vessel equipped with a stirrer.
The reaction system was stirred at 00°C so that the inside of the reaction system became uniform.

The temperature was further raised to 260°C, and the mixture was stirred for 1 hour under a pressure of 15 kg/c-. After that, the reaction was carried out under normal pressure for 2 hours while reducing the pressure and volatilizing the water from the reaction vessel. After the completion of the reaction, the reactant was taken out in the form of a strand from the lower nozzle of the reaction vessel, cooled with water, cut, and made into polyamide. A pellet consisting of a resin (average molecular weight 15.000) and montmorillonite was obtained.

The pellets were immersed in hot water to extract and remove unreacted monomers (about 10%), and then dried in vacuum to obtain a polyamide resin composition.

The following evaluation tests were conducted on the material thus obtained.

(1> Monofilament evaluation test The test material was put into an extruder under the following conditions, and the diameter was 1.47 mm.
Melt extrusion from a nozzle of size n+m8, cooled in cooling water at 7°C, stretched with a 10th roller, and further stretched at a drawing speed of 250°C with a take-up speed of the 20th roller 3.9 times that of the 10th roller. ), further, the take-up speed of the 30th-layer was set to 5 times that of the 10th-layer, and the stretching temperature was 300° C.), and finally the 40th-layer was taken off at the same take-up speed as the 30th-layer, The atmosphere temperature was set at 220° C. during that time and heat-fixed to obtain a monofilament.

(Extruder conditions) Screw diameter: 30mm Cylinder setting temperature: CI C2C3C4N”C22
0240260270260 The following evaluation test was conducted on the obtained monofilament.

l) Fineness 2) Tensile strength, elongation, elastic modulus JIS L1070
, Measured according to L1073 3) Pulling force Create the jig shown in Figure 1, measure the force with a load cell when pulling the filament from a 10 mm diameter hole with the key-shaped jig, and calculate the maximum value as the bow-drawing force. I used it as power.

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

(2) Multifilament evaluation test sample ■ Shimadzu spinning machine (screw diameter 30 m)
m%L/D=23, compression ratio 3.5), the company's winding machine (S
A multifilament was obtained by spinning and drawing-twisting using a draw-twisting machine (TS-1, surface drive system, 1 spindle bobbin) and a draw-twisting machine manufactured by the same company (SD-4).

The detailed conditions are as follows.

(Spinning conditions) l) Extruder setting temperature 2℃ C, Ca C, AD HD 210 230 250 260 260 2502
) Nozzle: Diameter 0.45mrn x 30 holes 3) Take-up speed: 700 m/m1n4) Filter: 40/40
/75/125/250/325 mesh 5) Cooling air speed: 0.6 m/s 6) Oil agent: 5pinner F-160 manufactured by Marukata Yuka ■
7S (drawn twisting conditions) 1) Stretching temperature = 170°C (hot bin) 2) Stretching ratio:
4 times 3) Drawing speed: 100 m/min In the above manner, a multifilament with a target of 240d/30f was created.

The following evaluation test was conducted on the obtained multifilament.

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

3) Visually evaluate the shine and glitter of the thread.

The results are shown in the table.

Example 2 In Example 1, 10 kg of ε was added to the reactor equipped with a stirrer.
An experiment similar to Example 1 was carried out, 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, lokg of ε-
An experiment similar to Example 1 was carried out, charging only caprolactam, 1 kg of water, and without adding the complex. The results are shown in the table.

4,

[Brief explanation of drawings]

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

Claims (1)

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