JPS58173154A - Production of impact-resistant polyamide - Google Patents

Abstract

PURPOSE:To produce a polyamide having improved impact resistance, by blending an ethylenic copolymer and an ethylene/propylene/non-conjugated diene copolymer rubber with a polyamide, and melt-kneading the mixture. CONSTITUTION:2-100pts.wt. ethylenic copolymer consisting of monomer units of ethylene, an unsaturated carboxylate ester [e.g. methyl(meth)acrylate], an unsaturated carboxylic acid [e.g. (meth)acrylic acid] and an unsaturated carboxylate metal salt[e.g. sodium (meth)acrylate], and 1-70pts.wt. ethylene/ propylene/non-conjugated diene copolymer rubber such as ethylene/propylene/ ethylidene-norbornene copolymer rubber, are added to 100pts.wt. polyamide such as nylon 6, nylon 11 or nylon 66. The mixture is melt-kneaded to produce a polyamide having improved impact resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of polyamide with excellent impact resistance.

Polyamides are generally characterized by their wear resistance, electrical properties, III
It has excellent thermal properties and mechanical strength, and is widely used as an engineering resin for various mechanical parts, but it has the drawback of insufficient impact resistance.

Hitherto, various studies have been conducted on methods for improving the impact resistance of polyamides, and one of them, 1-, has been proposed: a method of blending an ethylene copolymer with polyamides.

In a method for improving the impact resistance of polyamide using an ethylene copolymer.

We conducted extensive research with the aim of developing a method that can further improve impact resistance than known methods.

As a result, they found that the object could be achieved by blending an ethylene-propylene-nonconjugated diene copolymer rubber as the sixth component, and completed the present invention.

That is, the present invention uses 100 parts by weight of polyamide.

(a) 2 to 100 parts by weight of an ethylene copolymer consisting of one monomer unit of ethylene, an unsaturated carboxylic acid ester, an unsaturated carboxylic acid, and an unsaturated carboxylic acid metal salt;
(b) A new method for producing a polyamide with excellent impact resistance is provided, which comprises adding 1 to 70 parts by weight of an ethylene-propylene-nonconjugated diene copolymer rubber and melt-kneading the mixture.

The polyamide obtained by the production method of the present invention has extremely high impact resistance, and is also high even at low temperatures (retains four impact resistance).

Specific examples of polyamides used in the present invention include nylon 6, nylon 11. Polylactams such as nylon 12, nylon 66, nylon/610. Polyamides obtained from dicarboxylic acids and diamines such as nylon 612, nylon 6/66, nylon 6/61
0. Nylon 6/12, nylon 6/612. Nylon 6/66/610, nylon 6/66/12.
Examples include copolymerized polyamides such as nylon 6/6T (T: terephthalic acid component), mixtures thereof, and the like.

The polyamide preferably has a relative viscosity of 1, usually 2.6 to 6.0, when measured according to JIS-6810.

Furthermore, the ethylene copolymer used in the present invention is
Ethylene, unsaturated carboxylic acid ester.

It is a copolymer consisting of one monomer unit of an unsaturated carboxylic acid and an unsaturated carboxylic acid metal salt.
It can be produced according to the method described in Japanese Patent No. 4-4743. Unsaturated carboxylic acid ester has 5 to 8 carbon atoms
Lower alkyl esters such as acrylic acid, methacrylic acid, and 1-ethyl acrylic acid are preferred, and specific examples include methyl acrylate, ethyl acrylate, methyl methacrylate, and n-methacrylate.
Examples include butyl, methyl 1-ethyl acrylate, and the like. In addition, the unsaturated carboxylic acids/acids of the above types are useful,
As for the metal species of the metal salt.

Examples include sodium, potassium, magnesium, calcium, barium, and zinc.

This copolymer consists of unsaturated carboxylic acid ester (a mole), unsaturated carboxylic acid (b mole), and unsaturated carboxylic acid metal, in which ethylene accounts for 90 to 98 moles, and the remainder accounts for 10 to 2 moles. between salts (C mol).

(-) x 1o o, = 5~50■) [Especially 1
0 to 40 (branch))] a + b 10 and (-221) kari 00 = 5 to 90 (a) [especially 10 to a
s(%))a+b+c is preferable.

That is, a copolymer with ethylene content lower than the above ratio11.
It is difficult to manufacture, and if a copolymer with a higher proportion than the above is used, the +1liJ mountain impact resistance of the resulting polyamide is insufficiently improved. Furthermore, if the relationship between the unsaturated carboxylic ester, the unsaturated carboxylic acid, and its metal salt is outside the above range, the impact resistance of the resulting polyamide will not be sufficiently improved, and the fluidity and tensile strength during melting will be insufficient. It has poor physical properties such as 1f.

Furthermore, ethylene-propylene- used in the present invention
Non-conjugated diene copolymer rubber is ethylene.

It is a rubber-like copolymer consisting of one monomer unit of propylene and a non-conjugated diene. Specific examples of non-conjugated dienes include Iy:'i, 1,4-hexadiene, pentagene, dicyc']pentagene,
Methyltetrahydrointene.

Examples include methylene norbornene and ethylethene norbornene.

This copolymer rubber has 60 to 90 moles of ethylene units,
Preferably 50 to 85 molar ratio, 10 to 85 propylene units
70 mol., preferably 15 to 50 mol., and non-conjugated diene 0.01 to 10 mol., preferably 0.1 to 5.
Those containing mulch are effective.

The amount of the ethylene copolymer used is 2 to 100 parts by weight, preferably 5 to 70 parts by weight, per 100 parts by weight of the polyamide. Also, what is the amount of ethylene-propylene-nonconjugated diene copolymer rubber used?

1 to 70 parts by weight per 100 parts by weight of polyamide.

Preferably it is 2 to 50 parts by weight.

If the amount of these ethylene copolymers and ethylene-propylene-nonconjugated diene copolymer rubber used is less than the above-mentioned lower limit, sufficient impact resistance cannot be imparted to the resulting polyamide composition, and the above-mentioned When the amount exceeds the upper limit, the tensile strength of the resulting polyamide composition decreases, and the rate of decrease in heat distortion temperature increases.

There are no particular restrictions on the method of melt-kneading the ethylene copolymer and ethylene-propylene-nonconjugated diene copolymer rubber added to the polyamide. They may be melt-kneaded, or they may be added to powdered or pelleted polyamide and melt-kneaded. Alternatively, a mixture of an ethylene copolymer and an ethylene-propylene-nonconjugated diene copolymer rubber may be melt-kneaded with the polyamide.

The temperature during melt-kneading is usually 200 to 320°C, preferably 240 to 00°C.

Dyes, pigments, and fillers are added depending on the purpose during melt mixing of polyamide, ethylene polymer, and ethylene-propylene-nonconjugated diene copolymer rubber.

Nucleating agents, fibrous materials, plasticizers, lubricants 91 Foaming agents, heat resistant agents.

Appropriate amounts of weathering agents, flame retardants, etc. may be added.

Next, nine examples and comparative examples of the present invention are listed. On each side, the Izod impact strength of the molded product obtained is expressed as A
Measured according to STM'D256 (10 notched 1/2" test pieces).

Examples 1-5 Relative viscosity 2,9. Terminal carboxyl group concentration 1.7×1.
0'''5 equivalents/2.Terminal amine group concentration 8.5X10''''
Polyamide (nylon-6) 1o with 5 equivalents/f.

Weight: 94.6 mol% ethylene, 0.6 mol% methyl methacrylate, 2.2 mol% methacrylic acid, and magnesium salt of methacrylic acid (metal neutralization rate: 54%)
An ethylene copolymer consisting of one monomer unit of In each case, 40 parts by weight) were added and mixed.

The obtained mixture was melt-kneaded using a twin-screw extruder with a screw diameter of 30-0 under the conditions of 250°C, screw rotation speed of 200 rpm, and discharge rate of 6 Ky/hr, pelletized, and then vacuumed at 110°C for 24 hours. Dry.

The pellets were then injection molded into test pieces using a scree injection molding machine at a cylinder temperature of 270'C.

Table 1 shows the Izot impact strength of the molded products.

Comparative Example 1 An experiment was carried out in the same manner as in Examples 1 to 5, except that the ethylene-propylene-ethyritene norbornene synthetic rubber was not blended.

Table 1 shows the Izot impact strength of the molded products.

Table 1 Examples 6 to 10 The ethylene copolymer and the ethylene-propylene-ethylidenenorbornene copolymer rubber were added in a mixing ratio of 25 parts by weight based on 100 parts by weight of the polyamide. teeth.

Experiments were conducted in the same manner as in Examples 1 to 5.

Table 2 shows the Izot impact strength of the molded products.

Comparative Example 2 An experiment was conducted in the same manner as in Examples 6 to 10, except that the ethylene-propylene-ethyritene norbornene copolymer rubber was not blended.

Table 2 shows the Izot impact strength of the molded products.

Table 2 Examples 11 to 15 Polyamides with relative viscosity of 3.0. Examples 1 to 5 and An experiment was conducted in the same manner as in Comparative Example 1.

Table 6 shows the Izot impact strength of the molded products.

Experiments were conducted in the same manner as in Examples 11 to 15, except that the ethylene-propylene-ethyritene norbornene copolymer rubber was not blended.

The Izot impact strength of the molded product is shown in Table 2.

1 Table 6 Example 16
and 17 In place of the copolymer rubber in Examples 1 to 5, ethylene 7
Experiments were carried out in the same manner as in Examples 1 to 5, except that a predetermined amount of a copolymer rubber consisting of 8.4 mol.

Table 4 shows the h-Izot impact strength of the molded product.

Table 4

Claims (1)

[Claims] 2 to 100 parts by weight of an ethylene copolymer consisting of one monomer unit of (a) ethylene, an unsaturated 11-carboxylic acid ester, an unsaturated carboxylic acid, and an unsaturated carbonic acid metal salt to 100 parts by weight of BoIJ7 Mid.・(1.) Ethylene-propylene-nonconjugated diene copolymerization II, 1-
A method for producing impact-resistant polyamide, which comprises adding 70 parts by weight and melt-kneading.