JPS61283654A - resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. having greatly improved heat resistance, by blending a crystalline copolyamide with a filler. CONSTITUTION:A resin compsn. is obtd. by blending 99.9-85pts.wt. crystalline copolyamide composed of either 60-99wt% repeating unit of formula I and 40-1wt% repeating unit of formula II, or 60-99wt% repeating unit of formula I and 40-1wt% (II)+(III) with 0.1-65pts.wt. filler. Preferred examples of the fillers are silica, alumina, silica/alumina, titanium dioxide, molybdenum disulfide and polytetrafluoroethylene. The titled resin compsn. can be obtd. by melt- kneading a mixture of the filler and the copolyamide powder. If desired, additives such as antioxidant, heat stabilizer, ultraviolet absorber, lubricant, parting agent, dye, pigment, etc. may be added thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to hexamethylene diamine CIMDAx terephthalic acid (TA) and l-caprolactam (CL), or HMDA%TA%CL and either adipic acid (AA) or isophthalic acid (IA). The present invention relates to a crystalline copolyamide resin composition made from a mixture.

Conventionally, polyamide (nylon 6) from CL, HMDA
Polyamide (nylon 6.6) made from
They are 5°C and 259°C, and even if glass fiber is added, the limits of heat distortion temperature remain at the melting point.

Recently, as heat-resistant applications have increased, fully aromatic polyamides, polyamideimides, polyimides, polyethers, polyesters, etc. have begun to appear on the market, but they have poor workability and are expensive due to their raw materials. In addition, because the polymerization method is complicated, the price is several times higher than that of nylon 6, nylon 66, etc.

The present inventors have conducted intensive studies on resin compositions that have improved heat resistance than nylon 6 and nylon 66, are inexpensive raw materials, and can be melt-molded.
A/CL.

HMDA/TA/CL/IA or l(MDA/TA/C
Highly crystalline copolyamide consisting of L/AA and specific wave fillers, namely silica, alumina, silica alumina, alumina, talc, diatomaceous earth, clay, kaolin,
Quartz, Glass, Mica, Ceracola, Bengau, Graph 1
A resin composition containing carbon dioxide, titanium dioxide, molybdenum disulfide, zinc oxide, aluminum, copper, stainless steel, wollastonite, potassium titanate fiber, polytetrachloroethylene, or a mixture thereof is heated from about 240°C to about 810°C.
They discovered that it has a heat distortion temperature of 0, and that the heat resistance increases over a wide range of width, leading to the present invention.

In carrying out the present invention, f(MDA, TA).

The preparation ratio of CL, IA%AA is the following iterative component (Bl
-NH(CH2)sC- [it% or (A160-99% by weight, direction +
It is sufficient to prepare IC+40-11 so that the amount becomes %.

More preferable amounts are (A) 65 to 95% by weight, (B) 86
~5% by weight, or (A) 65-95% by weight,
(Bl-fc) 85-5%.

In the resin composition of the present invention, the amount of the above-mentioned crystalline copolyamide is 99.9 to 851! It is a quantity part. Preferably it is 99.5 to 50 jushabu. Also, the amount of filler is 0.1 to 65 parts by weight, preferably 0.5 parts by weight.
~50 parts by weight.

Specifically, the filler is 1. Silica, alumina, silica alumina, talc, diatomaceous earth, clay, kaolin, quartz, glass, mica, graphite, molybdenum disulfide,
Powdered and plate-like inorganic compounds such as Ceracola, Bengela, titanium dioxide, zinc oxide, wollastonite, potassium titanate fiber, aluminum, copper, and stainless steel; powdered and plate-like organic compounds such as polyfluoroethylene and polyethylene. Alternatively, a mixture thereof can be mentioned.

Preferred fillers include silica, alumina, silica-alumina, titanium dioxide, molybdenum disulfide, polytetrafluoroethylene, and the like.

In particular, when graphite, molybdenum disulfide, or polytetrachloroethylene is used, the wear resistance of the molded article obtained from the composition, such as the coefficient of dynamic friction, taper wear, and limit Pv value, is improved. The average particle size of such fillers is usually 0.
．． It is in the range of 1 mμ to 200μ, particularly in the range of 1 mμ to 100μ, and the wear resistance is significantly improved.

An appropriate amount of inorganic or organic FIA fibers such as gelatin fiber, carbon fiber, mineral fiber, etc. can also be added to the resin composition.

The resin compositions of the present invention may be made by any conventional method. For example, the filler can be combined with the granulated copolyamide and the resulting mixture can be melt-kneaded in a conventional extruder, kneader, or the like. At that time, an appropriate amount of antioxidant, heat stabilizer, ultraviolet absorber, lubricant, mold release agent, colorant such as dye and pigment, flame retardant, flame retardant aid, and electrostatic charge are added to the resin composition of the present invention. Add ordinary additives such as inhibitors to 1[[
You may add more than that.

The method for producing the copolyamide of the present invention is not particularly limited, and may be either continuous or batch polymerization, and methods such as heating and polymerizing raw materials under pressure, normal pressure, or reduced pressure can be employed. For example, the nylon salt of HMDA-TA is
Strain 1 of the 0 to 60 wt. Then, water vapor is removed and polymerization is carried out at normal pressure for 80 minutes to 4 hours. Of course, during polymerization, various additives such as polymerization degree regulators, heat stabilizers, weather resistance agents, antistatic agents, pigments, and flame retardants may be added.

As another manufacturing method, a method in which the prepolymer is divided into a part and a final polycondensation part is also preferable. The prepolymer portion may be batch, batch-continuous, or fully continuous, consisting of one or more agitated tank reactors of suitable design. The prepolymer product at this stage is a copolyamide oligomer with a reduced viscosity (a sulfuric acid 80° C.) of 0.1 to 0.8 d(1/f).

Batch production of the prepolymer may be carried out in any suitably designed stirred reactor capable of handling high viscosity materials. 80% of the feedstock material consisting of acid, amine and additives.
Load the reactor at °C. The water content of the resulting solution should not be more than 15% by weight. The temperature is then increased as quickly as possible to 280-800°C. After reaching the target temperature,
Collect pressure from 5 to 120. The prepolymer is then ground and fed to the final polycondensate.

Prepolymers can also be produced by the following method. The salt or prepolymer, which is readily sprayed with a control means that provides an aerosol mist, is condensed at about 0-80 atmospheres, wherein the polymerization is carried out at a wall temperature of about 200°C to about 50°C and about 170°C to about 400°C. Examples include methods carried out in a flash reactor designed to provide a high amount of heat transfer at a melting temperature of 0.degree. It will be done.

The heat distortion temperature of the composition is about 240°C to about 8□oc7. It's normal 9. Characteristics 7. This is completely unexpected from conventional methods. The importance of high heat distortion temperatures allows for use in applications such as automotive roofs, lawn mower shrouds, chainsaw protectors, and electrical connector equipment. Besides the heat distortion temperature, the tensile strength is high, which is comparable to or higher than die-cast aluminum or zinc, while the specific gravity of the copolyamide of the present invention is about half that of aluminum or zinc.

The invention will be illustrated with reference to the following examples.

Examples 1 to 5, Comparative Examples 1 to 8 50% aqueous solution of HMDA/TAt-ylon salt, CL, H
50% aqueous solution of nylon salt of MDA/IA and HtV
A 50% aqueous solution of ID A/AA nylon salt was charged into a polymerization reactor dζ at the composition ratio shown in Table 1, respectively. After the reactor was completely purged with nitrogen gas, it was heated, and polymerization was carried out at 240°C to 260°C while keeping the water vapor pressure at 10.0°C. Further, after the processing, water vapor was removed and polymerization was carried out at normal pressure for 2 to 4 hours.

The obtained polymer was sufficiently cooled and taken out, pulverized using a pulverizer, and then sufficiently dried at 90° C. or lower so that the moisture content was 0.1% or lower. The reduced viscosity of this prepolymer is o, 15 aeit (concentrated ffl acidic acid C=O, l
/100cc measured at 80°C). The dried polymer was reacted in a twin screw extruder with one or more vents and cut into pellets. The temperature of the extruder is 820~aaO
C, screw rotation speed 10-20 r, p, m, average retention time of the polymer 5-10 minutes, and the hopper mouth was under a nitrogen atmosphere. The vent hole can be opened to either reduced pressure or normal pressure, and the polymer coming out of the extruder nozzle was immediately cooled by putting it in water to keep it from coming into contact with air at a light temperature. The obtained polymer pellets were sufficiently dried at 90°C or lower so that the moisture content was 0.1% or less (reduced viscosity was 1.Od).
6/f), the mixture was blended with a filler in the composition shown in Table 1, and granulated using a twin-screw extruder.

The granulation temperature is approximately 800°C to 340°C.

Then, injection pressure t is applied to the ivy mold kept at about 100 to 200°C.
Injection at o o ox, barrel temperature 800-850℃
Met.

Example 6 Crystalline copolyamide polymerized from 80 parts of nylon salt of HMDA/TA and 20 parts of CL (reduced viscosity bi 1.0
dll/f), 40 parts of talc, and 20 parts of titanium oxide were granulated at 840°C using a twin-screw extruder.

The heat distortion temperature of the injection molded product was 280° C. or higher, and a composition with small anisotropy, good fluidity, and excellent appearance was obtained.

Example 7 In Example 6, injection molding was carried out in the same manner as in Example 6, using 20 parts of potassium titanate fiber instead of titanium oxide. A composition with a heat distortion temperature of 280° C. or higher and an excellent appearance was obtained.

Claims (1)

[Claims] 1) The following repetitive components (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (C) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is -(CH_2)_4- or ▲ mathematical formula, chemical formula,
There are tables etc. Represents ▼. ), consisting of (A) 60-99% by weight and (B) 40-1
(A) 60-99% by weight, (B)
+A resin composition comprising 99.9-35 parts by weight of a crystalline copolyamide comprising 40-1% by weight of (C) and 0.1-65 parts by weight of a filler.