JPS61108659A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having a high heat distortion temp. and greatly improved heat resistance, consisting of a crystalline copolyamide and glass fiber, glass bead, mineral fiber, carbon fiber or arom. polyamide fiber. CONSTITUTION:A resin compsn,. consists of 95-35pts.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% of repeating unit of formula II + repeating unit of formula III and a filler. Said filler is glass fiber, glass bead, mineral fiber, carbon fiber, arom. polyamide fiber or a mixture thereof. In the formula, R is -(CH2)4 or a group of formula IV. Particularly preferred filler is glass bier, which is prepd. from alkali-free borosilicate glass or alkali-contg. C glass.

Description

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

Conventionally, polyamide (nylon 6) from CL, HMDA
Polyamide (nylon 6.6) made from
℃ and 259℃, but even if lath fibers are added, the limit of heat distortion temperature remains 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 processability, and the raw material monomers are expensive. Because the polymerization method is complicated, it is several times more expensive than 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 HMDA/
A resin composition containing a highly crystalline copolyamide consisting of TA/CL/AA and a specific amount of glass fiber, laspeed, mineral fiber, carbon fiber, aromatic polyamide, or a mixture thereof can be heated from about 240°C to about 810°C.
They have achieved a resin composition that has a heat deformation temperature of °C and has greatly improved heat resistance.

In carrying out the present invention, HMDA, TA.

The preparation ratio of CL and IAlAA is the following repetitive component B)
-NH(cu2.), c-, 460-99% by weight, β140-1% by weight, or 760-99% by weight, (Bl+(C140
-1% by weight.

More preferred amounts are 65 to 95% by weight, (B) 85 to 5
% by weight, or (A165-95% by weight, G
) 36-5% heavy failure.

In the resin composition of the present invention, the amount of the above-mentioned crystalline copolyamide is 95 to 35 parts by weight. Preferably 90
~40 parts by weight.

The amount of filler is 5 to 65 parts by weight, preferably 10 to 60 parts by weight. The filler may include lath fibers, laspeed fibers, mineral fibers, carbon fibers, aromatic polyamide fibers, or mixtures thereof. Suitable fillers include glass fibers such as Laspeed, Glass sphere, Glass cloth, titanate potash fiber, PAN fiber, pitch fiber, aromatic boria-mide fiber Kevlar (manufactured by DuPont). ) and HM-50 (manufactured by Kaneiri). A preferred filler is glass fiber. These are made of alkali-free borosilicate lath or alkali-containing C lath. Preferably, the fiber thickness is on average between 8 and 80 microns. It is possible to use long fibers ranging from 5N to 50N, and each
．． Short fibers with filament lengths of 0.5 m to 5 m are also possible. Laspeed, which has a diameter in the range of 5 microns to 50 microns, may also be used as a reinforcing material.

The reinforced copolyamide may be applied by any conventional method. It is suitable to coat so-called rovin dust strands of uncut but lath fibers with a copolyamide melt and then to granulate them. Advantageously, the cut fibers and Laspeed may be combined with the granulated copolyamide and the resulting mixture melted in a conventional extruder, or alternatively the fibers may be introduced into the copolyamide as appropriate. It may be melted in the extruder through an inlet.

The method for producing the copolyamide of the present invention may be either continuous or batch polymerization, and methods such as heating and polymerizing raw materials under pressure, normal pressure, or reduced pressure may be employed. 30-60% by weight
It is made into an aqueous solution, charged into a polymerization reactor together with CL, and after the reactor is completely replaced with nitrogen gas, it is heated and the water vapor pressure is 5 to 5.
It is sufficient to react at a temperature of 250 to 270 C while maintaining the temperature at 101/d, and then polymerize for 30 minutes to 4 hours at normal pressure after removing water vapor.

During polymerization, polymerization degree regulators, heat stabilizers, weather resistance,
Various additives such as 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 has an intrinsic viscosity (60/40 phenol/TC at 0 DEG C.) of 0.2 (1/f (7)).

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 raised to 250-810°C as quickly as possible. After reaching the target temperature,
The pressure is reduced to atmospheric pressure over a period of 5 to 120 minutes.

The polymer is then discharged from the reactor under an inert atmosphere and the prepolymer can also be prepared as follows. Approximately 0
condensing salts or prepolymers that are readily sprayed with controlled means to provide an aerosol mist at -80 atmospheres, wherein the polymerization is at a wall temperature of about 200°C to about 500°C and a melt temperature of about 170°C to about 400°C; carried out in a flash reactor designed to give a high amount of heat transfer,
and a method comprising holding the polymer in the reactor for about 0.1 seconds to about 80 seconds.

The heat distortion temperature of the composition is from about 2400 to about 810°C, which is an unusual feature and 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 1-4, Comparative Examples 1-8 50% aqueous solution of HMDA/TA nylon salt, CLXHM
50% aqueous solution of nylon salt of DA/IA and HMDA
A 50% aqueous solution of /AA nylon salt was charged into a polymerization reactor at the composition ratio shown in Table 1. After completely purging the reactor with nitrogen gas, it was heated to bring the water vapor pressure to 8.5KII/
Polymerization was carried out at 260°C to 270°C. Further, after the processing, water vapor was removed and polymerization was carried out at normal pressure for 30-4 hours. The obtained polymer was spun into water and then cut into pellets.

The pellets were then dried to a moisture content of 1% or less, blended with glass fibers in the composition shown in Table 1, and granulated using a twin-screw extruder. Granulation temperature is approximately 290
~340°C.

Next, the injection pressure was 1000Kf/- into a mold kept at about 100 to 200℃, and the barrel temperature was 300 to 850℃.
It was warm at ℃.

Procedural amendment (1 letter) February 26, 1985 2. Name of the invention Resin composition 3. Relationship with the person making the amendment Patent applicant address 5-15 Kitahama, Higashi-ku, Osaka Name (
209) Sumitomo Chemical Co., Ltd. Representative: Takeshi Hijikata 4 Address: 5-15-5 Kitahama, Higashi-ku, Osaka City, 5-15-5 Kitahama, Higashi-ku, Osaka, Japan Please fill in the column for the detailed explanation of the invention in the specification to be amended and the description of the contents of the amendment as follows. Correct accordingly.

(1) “30 minutes” on the fifth line from the bottom of page 6 is “0.5J.”

(2) “0.1 to 0.26i” in the 6th to 8th lines from the top of page 7
/11 intrinsic viscosity (60/40 phenol/TCE, 3
0'C)J is "0.1 to 0.3 (it/11 intrinsic viscosity (30°C in concentrated sulfuric acid)").

(3) Set "30" in the 8th line from the bottom of page 9 to rO,5J.

(Table 1 on page 4111 is amended as follows.

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)
+95-35 parts by weight of a crystalline copolyamide consisting of 40-1% by weight of (C), glass fibers, glass beads,
A resin composition comprising 5 to 65 parts by weight of mineral fiber, carbon fiber, aromatic polyamide fiber, or a mixture thereof.