JPH0324155A - Polyamide blow molding material - Google Patents

Abstract

PURPOSE:To obtain a polyamide blow molding material having excellent blow moldability, rigidly, dimensional stability and surface smoothness and being desirable for products such as pots, tanks and air ducts by mixing a polyamide resin with a layered silicate. CONSTITUTION:A polyamide blow molding material is obtained by mixing 100 pts.wt. polyamide resin (desirably one of an average mol.wt. of 25000-35000, e.g. nylon 6) with 0.05-30 pts.wt. layered silicate of a thickness of 6-20Angstrom and a side of 0.002-1mum, e.g. montmorillonite.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention relates to a polyamide blow molding material, and more particularly, the present invention relates to a polyamide blow molding material, which has excellent blow molding properties, and has good rigidity, dimensional stability, and This article relates to a polyamide blow molding material with surface smoothness. (Prior Art) Polyamide resins have excellent mechanical and thermal properties and are widely used in blow molded products such as bottles, tanks, air ducts, and hollow pipes. However, in order to adapt the melt viscosity characteristics of polyamide resin to blow molding processing, the resin must have a high molecular weight, but it is technically difficult to produce such a resin, so generally, Should olefin resin be mixed? (Japanese Patent Publication No. 55-4 1 659). Polyamide is thickened by mixing glass fiber (JP-A-60-171133) to improve its blow molding properties. However, thickening with olefin resins results in lower heat resistance and lower chemical resistance, which limits the fields in which they can be used. In addition, although thickening with glass fiber improves blow molding properties and mechanical properties, it also causes the surface condition of the molded product to be rough and the appearance, especially the surface smoothness of the inner surface not in contact with the mold, to be poor. There were problems with parts through which gas flows, such as ducts and intake manifolds, such as noise generation. (Problems to be Solved by the Invention) “The present invention improves the above-mentioned problems of polyamide blow molding materials, and provides excellent blow molding properties, as well as rigidity, dimensional stability, heat resistance, and surface smoothness. It is an object of the present invention to provide an excellent material for blow molding. [Structure of the invention] (Means and effects for solving the problems) The present invention provides a polyamide resin (A) Zoo weight part and a layered silicate (B) 0.
This is a polyamide blow molding material consisting of 0.05 to 30 parts by weight. The polyamide resin (A) is a polymer having an acid amide bond (-CONH-) in the molecule, and specifically includes ε-cabrolactam, 6-aminocaproic acid, ω-enantholactam, 7-aminohbutanoic acid. , l1-aminoundecanoic acid, 9-aminononanoic acid, α-virolidone,
Polymers or copolymers obtained from α-biveridone etc.:
Polymers obtained by polycondensation of diamines such as hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, metaxylylene diamine, and dicarboxylic acids such as terephthalic acid, isophthalic acid, adivic acid, and sebacic acid. or a copolymer or a blend thereof. The average molecular weight of the polyamide resin (A) is 25.000~
35,000 is preferred. If the average molecular weight is less than 25,000, the blow molding properties will deteriorate, and if it is more than 35,000, it will become difficult to produce the polyamide itself, which is not preferable. The layered silicate (B) provides the polyamide resin (A) with excellent blow molding properties, excellent mechanical properties, and heat resistance without impairing its surface properties. When dispersed in component (A), the layered silicate (B) preferably maintains an average glabellar distance of 20 or more and is uniformly dispersed. Here, the interlayer distance 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 that a multilayer structure 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. Therefore, a layered silicate refers to a unit of material with a thickness of 6 to 20 mm and a side of 0.002 to IF. 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, paidelite, nontronite, hectorite, and stipunsite, as well as vermiculite and halloysite, which are natural and 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 0.05 to 30 parts by weight per 10 parts by weight of component (A). (B) The composition of the component is 0
．． If it is less than 0.05 parts by weight, the improvement in blow molding properties, mechanical properties, heat resistance and dimensional stability of the material will not be noticeable, and if it exceeds 30 parts by weight, production will become difficult, which is not preferable. ．． The material for molded products of the present invention may include dyes, pigments, fibrous reinforcing agents, particulate reinforcing agents, plasticizers, heat resistant agents, blowing agents, etc. depending on the purpose.
Flame retardants, impact modifiers, crosslinking agents, etc. can be added in appropriate amounts. Although the method for producing the material for molded articles of the present invention is not particularly limited, for example, the following method can be applied. When the layered silicate (B) is a multilayered clay mineral, it is brought into contact with a swelling agent to expand the interlayers in advance to facilitate the incorporation of monomers between the layers, and then mixed with a polyamide monomer and polymerized (in particular). (Refer to Kaisho 62-74957)
It is. Alternatively, a method may be used in which a polymer compound is used as a swelling agent, the space between the layers is increased to 20 or more, and this is melt-kneaded with a polyamide resin or a resin containing the same to uniformly disperse it. The polyamide blow molding material of the present invention is suitable for parts or products formed by blow molding, such as various tanks such as gasoline tanks and oil tanks, various bottles such as pesticide bottles and drinking water bottles, air ducts, and intake manifolds. Suction and exhaust system parts for each F1 machine and automobile, etc.
Automotive exterior panels such as air spoilers, fenders, bumpers, etc.
It can be used for applications such as exterior structural members. (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. 100g of IF montmorillonite
The mixture was dispersed in 0β water, and 51.2 g of 12-aminododecanoic acid and 24M1 concentrated hydrochloric acid were added thereto, stirred for 5 minutes, and filtered. After thoroughly washing this, it was vacuum dried. Through this operation, a composite of ammonium 12-aminododecanoate and montmorillonite was prepared. The layered silicate content in the composite was 80% by weight. Next, 10 kg of ε-1 turnip lactam, 1 kg of water and 200 g of the above complex were placed in a reaction vessel equipped with a stirrer,
The reaction system was stirred at 100°C to maintain a homogeneous state. The temperature was further increased to 260"C, and 15 kg/
The mixture was stirred for 1 hour under a pressure of
2 hours under normal pressure while evaporating water from the reaction vessel.
The reaction was carried out for 1 hour at a vacuum level of 250 Torr. After the reaction was completed, the reactant was taken out in the form of a strand from the lower nozzle of the reaction vessel, cooled with water, and cut to obtain a pellet made of polyamide resin (average molecular weight 30.000) and montmorillonite. This pellet was immersed in hot water to extract and remove unreacted monomer (approximately 10%), and then dried in vacuum to obtain a blow molding material of the present invention. The following evaluation tests were conducted on the material thus obtained. The results are shown in the table. l) Mechanical property evaluation The following mechanical properties and thermal properties were measured for specimens injection molded under the following conditions. Injection molding conditions> Injection molding machine: Toshiba Machine IS-80 Cylinder setting temperature: C + 240°C: C8260°C; 270
°C: C4 (nozzle) 270 °C Injection pressure: 600 kg/cra'' Mold temperature:
88°C Injection time: lO seconds Cooling time = 20 seconds Tensile yield point strength: ASTM D-838 Elongation at break ASTM D-638 Flexural modulus: ASTM D-790 This was done in a dry state. Heat distortion temperature + ASTM D-648 Tested in an absolutely dry state. 2) Surface roughness: 220 mm x 120 mm from the sample under the following conditions
A hollow box of mm x 50 mm and wall thickness of 1.5 mm was created, and the smoothness of its inner surface was measured. <Blow molding conditions> Blow molding machine: Extruder manufactured by Ube Industries ■, diameter 50 mm Balison controller manufactured by Moog Japan Resin temperature: 240°C Mold temperature 280°C Blow pressure: 6 kg/cm"G Die diameter: 90 questions <Smoothness Measurement method> Smoothness was measured using a surface roughness meter using the following method. (Apparatus) Universal surface profile measuring instrument SE-3C manufactured by Kosaka Institute ■Method: The roughness curve was measured using the above device. The surface smoothness (roughness) was determined from the width of the wave of the curve.3) Blow molding characteristics evaluation test Blow molding was performed using the following blow molding machine and molding conditions, and extrusion times were 10 seconds and 20 seconds. , measure the length of each balisong after 30 seconds, and evaluate the hollow molding characteristics (drawdown properties).
was evaluated. This test evaluates the drawdown properties of the balisong, and it is preferable that the balisong length changes linearly with time. <Blow molding conditions> Blow molding machine Extruder: Screw diameter 50 mm Screw rotation speed + 8 Orpm Gouy diameter: Outer diameter 73 mm Inner diameter 68 mm Molding temperature = 240°C Example 2 In Example 1, a composite of ammonium 12-aminododecanoate and montmorillonite The same experiment as in Example 1 was conducted except that the amount added was 300 g. The results are shown in the table. Example 3 In Example 1, an experiment similar to Example 1 was conducted except that the amount of the composite added was 400 g. The results are shown in the table. Comparative Example 1 An experiment similar to Example 1 was conducted using a material that was polymerized without adding the composite. The results are shown in the table. Comparative Example 2 The same experiment as in Example 1 was conducted using a material in which 25 parts by weight of glass fiber were added and mixed with 100 parts by weight of the polyamide resin of Comparative Example 1. The results are shown in the table. Comparative Example 3 To 100 parts by weight of the polyamide resin of Comparative Example 1, Isainomer resin (Himilan 81855) was added as a thickener.
An experiment similar to Example 1 was conducted using a material in which 35 parts by weight of . The results are shown in the table. [Effects of the Invention] The polyamide blow molding material of the present invention is a composition that has superior blow molding properties compared to conventional materials, as well as rigidity, dimensional stability, and surface smoothness. Therefore, its characteristics greatly contribute to the various uses mentioned above.

Claims (1)

[Claims] 100 parts by weight of polyamide resin (A) and layered silicate (B)
A polyamide blow molding material comprising 0.05 to 30 parts by weight.