JPH02286741A - Impact-resistant amorphous resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in elongation at break and impact resistance without detriment to its heat resistance and appearance by mixing an amorphous copolyamide with an acid anhydride-olefin copolymer of a specified MFR value. CONSTITUTION:50-10mol% isophthalic acid is reacted with 0-40mol% terephthalic acid, 45-5mol% hexamethylenediamine and 5-45mol% bis(4-amino-3- methylcyclohexyl)methane to obtain an amorphous copolyamide (A) of a relative viscosity (as measured in a 1wt.% m-cresol solution of a copolyamide) of 1.2. Separately, an unsaturated dicarboxylic acid anhydride is copolymerized with a polyolefin or an olefin polymer to obtain an acid anhydride-olefin copolymer (B) of an MFR value (at 190 deg.C under a load of 2160g) of 0.1-5.0g/10min. 60-95wt.% component A is mixed with 40-5wt.% component B.

Description

Detailed Description of the Invention (Industrial Field of Application) Amorphous resin composition of an amorphous copolyamide and (B) a polyolefin or acid anhydride-containing olefin copolymer having a specific MFR value It is related to.

[1] The amorphous PA resin of the present invention has excellent moisture resistance.

Due to its mechanical and thermal properties as well as its improved impact resistance, it is applied to a wide range of fields such as automobiles, electrical, electronic machinery, etc. through injection molding, extrusion molding, blow molding, etc.

(Prior art) Isophthalic acid (part of which can be replaced with terephthalic acid if necessary), hexamethylenediamine and bis(4-
Amorphous copolyamides obtained from amino-3-methylcyclohexyl)methane are known.

Such an amorphous copolyamide is transparent, has high heat resistance, and has excellent chemical resistance, and is expected to have a wide range of uses as a material for 1.j small molding, extrusion molding, and blow molding. For example, the amorphous JI:polymerized polyamide shown in Reference Example I exhibits a high heat distortion temperature and good strength and modulus. In addition, there is very little dimensional change due to water absorption in Nylon J'G and Nylon 66, and almost no change in terms of strength, strength, and elastic modulus compared to C. It has extremely excellent properties that are not found in common polyamides, and has very important applications.

However, what about the elongation at break and the impact? Impact strength, which is represented by strength, is not necessarily a satisfactory performance.

Materials with low values of these properties tend to be susceptible to brittle fracture and often have poor practical durability. Therefore, it is very important to improve the elongation at break and the impact strength by 1-1 from the practical viewpoint of materials, and this term also refers to the amorphous property.
Synthetic polyamides are no exception.

Many attempts have been made to improve the impact strength of common copolyamides. For example, JP-A-5051155 discloses a method of blending an ionomer. In JP-A-55412261'';'r publication, modified A[l
A method of compounding S resin is disclosed. However, even if these methods are applied to the amorphous copolyamide, the effect of improving impact strength is not necessarily sufficient, and the heat distortion temperature under large load and small load, which is one index of heat resistance, is not necessarily sufficient. A decrease is seen. In addition, molded products using these materials tend to become cloudy and have poor appearance. In this way, for copolyamide, appearance 1 and i4 thermal properties are 1
The reality is that all attempts to greatly improve fffiF& resistance without falling to zero have failed.

(Problem B to be Solved by the Invention) In view of the above circumstances, an object of the present invention is to improve the elongation at break and impact strength of a specific amorphous copolyamide without impairing its excellent heat resistance and appearance. The object of the present invention is to obtain an improved and useful amorphous resin silk composition.

(Means for Solving the Problems) In order to solve the above problems, the present inventors have conducted extensive research and found that (8) an amorphous copolymer polyamide and (Il) have a specific liver 17 value. A resin S, tl composition comprising a polyolefin or an acid anhydride-containing olefin copolymer satisfies the object of the present invention. I¥! i5! This is what led to the present invention.

That is, the present invention provides (8) 50 to 10 mol % of isophthalic acid, 0 to 40 mol % of terefucuric acid, 45 to 5 mol % of -.kyrimethylenediamine, and 5 mol % of bis(4-amino-93methylcyclohexyl)methane. ~45% by weight of an amorphous copolymerized polyamide obtained from 60 to 95% by weight h・1%, and (
B) Obtained by copolymerizing polyolefin or olefin copolymer with unsaturated dicarboxylic acid anhydride,
°C5 load 21GOg Nikkel MFL? Value is 0.1-5
．． Amorphous tree 11 consisting of 40 to 5% by weight of a polyolefin or acid anhydride-containing olefin copolymer in the range of h/10 min! I & II products are summarized.

In the amorphous copolyamide used in the present invention, a diamine component and a dicarboxylic acid component are first reacted in water to form a salt, which is then concentrated and polycondensed by a known method. The salt solution is preferably pre-condensed under reaction pressure in the range of 200-300'C in a closed autoclave, then the pressure is released and the polycondensation is exposed to atmosphere until equilibrium is reached. Carry out the reaction under reduced pressure.

In order to obtain good physical properties, the relative viscosity of the amorphous copolyamide (defined at 20°C using a 1v volume % m-cresol solution of the copolyamide) is 1.2 to 1. 8
It is desirable that it be within the range of . In order to adjust the relative viscosity of the amorphous copolymer polyamide, it is also possible to add known functional amines or carboxylic acids during the polymerization.

The copolyamide thus obtained is amorphous, exhibits no melting point, and is completely transparent and colorless.

The polyolefin as used in the present invention refers to a homopolymer of olefins such as polyethylene, polypropylene, polybutene-1, methyl methacrylate, ethyl methacrylate,
Butyl methacrylate 5 Methacrylic acid ester polymers such as 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, ethyl acrylate, butyl acrylate.

It refers to polymers of acrylic esters such as 2-edylhexyl acrylate and 2-hydroxyethyl acrylate.

The olefin copolymer referred to in the present invention refers to ni-f-lene-propylene copolymer, ethylene-butene 1 copolymer,
Ethylene-vinyl acetate copolymer, ethylene-propylene-diene J (copolymers of Tatsumi type olefins such as polymers or olefins and other different types of single solids such as acrylic jQff esters). The copolymer may be a random copolymer, a block copolymer, a graft copolymer, or an alternating copolymer.

The unsaturated dicarboxylic acid anhydride referred to in the present invention includes α,β-unsaturated dicarboxylic acid anhydride and alicyclic carboxylic acid anhydride having a cis-type double bond in the ring. Examples of α,β-unsaturated dicarboxylic acid anhydrides include maleic anhydride, chloromaleic anhydride, citraconic anhydride, and itaconic anhydride.

Examples of alicyclic carboxylic acid anhydrides having a cis-type double bond in the ring include cis-4-cyclo-xene 1,2-dicarboxylic acid, endo-bicyclo-[22, l'1-5-to Butene-2,3-dicarboxylic acid, methyl-endo-cis-bicyclo-C2,2,13-5-/butene-2,3-
Dicarboxylic acid, endo-bicyclo-C2,2,1]-L
2,3,4,7.7-hexachloro2-heptene-5,
There are anhydrides such as 6-dicarboxylic acid, and if necessary, functional derivatives thereof, such as metal salts, esters, amides, and acid halides of dicarboxylic acid 3 can also be used.

Examples of the acid anhydride-containing olefin copolymer 7 used in the present invention include 1,000-thin propylene copolymer, ethylene-butene-1 copolymer, ethylene-vinyl acetate copolymer,
Maleic anhydride or endorbicyclo-C22,1)-5-heptene-2,3-dicarboxylic acid to ethylene-propylene-diene copolymer, ethylene-acrylic acid ester copolymer and ethylene-methacrylic acid ester copolymer Copolymers or graft adducts of the anhydrides of are advantageously used.

The MFR4 direct referred to in the present invention is based on ASTM D 123.
Using the equipment specified in Section 8, a load of 2160g is applied at 190°.
The value calculated by cutting out the sample extruded within the time specified in C, placing it on top of each other, and converting it into the amount of flow for 10 minutes.
'1st place is given as (g/10min). MFII
(It is desirable that the direct current is in the range of 0.1 to 5.0 g/10 min. M17R (I'1' is 0.1 g/min
If it is less than n, the impact resistance will be improved, but the appearance will be poor.+5.
If it is less than 0 g/min, the heat resistance will be inferior to 191 and there will be no impact resistance improvement effect.

In addition, the blending amount of the acid anhydride-containing olefin copolymer is 5 to 5.
It is desirable that the weight be within the 40 weight range.

If it is less than 5% by weight, the impact strength is not significantly improved, and if it exceeds 40% by weight, the appearance and heat distortion temperature are significantly reduced.

To the resin composition of the present invention, one or more of various additives such as a fuel agent, a heat stabilizer, a lubricant, etc. may be added depending on the use and purpose within a range that does not adversely affect the original physical properties of the resin. I can do it.

As a compounding method for obtaining the resin composition according to the present invention, a method in which a predetermined amount of a mixture of amorphous copolyamide and polyolefin or olefin copolymer is directly introduced through a bopper port and injection molded; Melt-knead the amorphous copolyamide and polyolefin or olefin copolymer using a single-screw or multi-screw extrusion cup while weighing each with a measuring device such as a screw feeder, table feeder, or bell 1-feeder. A known method can be used, such as extruding a strand and using a cutter to form a pellet into injection molding.

Reference example 1: Amorphous copolymerized polyamideisophthalic acid 45% by weight, terephthalic acid 5% by weight hexamethylenediamine 45% by weight, bis-(4amino-3-
Methylcyclohexyl) methane 5% by weight, acetic acid 0.01
10 kg of raw materials containing 5% by weight were charged into a reaction tank together with 81 g of pure water, and the air in the reaction tank was purged several times with nitrogen. After raising the temperature to 90°C and reacting for about 5 hours, the reaction temperature was gradually increased to 280°C for 10 hours while stirring the tank under pressure (1B/<-R). Got it.

Then, the pressure was released and the pressure was lowered to atmospheric pressure, and then polymerization was further carried out at the same temperature for 6 hours. After the reaction was completed, it was discharged from the reaction vessel and cut to obtain pellets. The relative viscosity of the pellets obtained (same method as above) was 1.50. Further, the glass transition temperature was 150''C. This amorphous bowl polymerized polyamide is designated as PΔ-1.

(Example) Example 132. Comparative Examples 1 to 3 The A component was P8-1, and the B component had an MFIr value of 0.
071.5.3.8.5.7B/l0min acid anhydride-containing olefin copolymer was blended at the compounding ratio shown in Table 2, and then melted at 250'C using a twin-screw extruder. After kneading, extruding and cutting, the pellets were dried in vacuum at 100 °C for 15 hours. The temperature, rigidity, Izod impact strength and gloss of the molded product surface were evaluated.The measurement results are listed in Table 2.

l'4ff of Table 11 (τp combined polypolyamide 8-1)
q (Effects of the Invention) As specifically shown in the Examples, the amorphous resin composition of the present invention has significantly improved mechanical strength compared to the copolyamide alone. Furthermore, the thermal deformation temperature decreases little and the appearance is extremely good.

Among the comparative examples in which the ionomer was blended, there was no example in which the impact strength, heat distortion temperature, and appearance were well-balanced.

Patent applicant: Unideka Co., Ltd. Procedural master's letter (spontaneous) 1989 September 28th

Claims (1)

[Claims] (1) (A) 50 to 10 mol% of isophthalic acid, 0 to 40 mol% of terephthalic acid, and 45 to 5 mol% of hexamethylene diamine
60 to 95% by weight of an amorphous copolyamide obtained from 5 to 45 mol% of bis(4-amino-3-methylcyclohexyl)methane; and (B) an unsaturated polyolefin or olefin copolymer. Polyolefin or acid anhydride-containing olefin copolymer obtained by copolymerizing dicarboxylic acid anhydride and having an MFR value of 0.1 to 5.0 g/10 min at 190°C and a load of 2160 g 40 to 5 weight An amorphous resin composition consisting of %.