JPH021847B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an elastic thermoplastic polyamide composition and another thermoplastic polyamide composition obtained by blending the same. Specifically, polyamide elastomers modified with polyolefin resins, aliphatic α,ω-aminocarboxylic acids having 10 or more carbon atoms in the methylene chain, or lactams thereof, and/or aliphatic A polyamide obtained by polymerizing a diamine dicarboxylate salt in which at least one of a diamine and an aliphatic dicarboxylic acid has 10 or more carbon atoms in a methylene chain.
A highly tough polyamide-based thermoplastic resin composition can be obtained by incorporating it into a blend composition consisting of a homopolymer and/or polyamide copolymer and a polyolefin-based copolymer resin. In recent years, various thermoplastic elastomers have been developed, and as part of these, polyamide-based thermoplastic elastomers have also been developed, but they are inevitably expensive due to their manufacturing method. In addition, many compositions made of polyamide and polyolefin resin have been proposed from a practical standpoint, and among polyolefin resins, ethylene/vinyl acetate copolymer resin (EVA), ethylene/acrylic acid copolymer resin, etc. Although the compatibility with polyamide is relatively improved because the molecule contains a polar group, the range of compositions that can be mixed and blended with polyamide is limited. If it is added in excess of 30% by weight, the toughness will be impaired, and in particular if it is added in excess of 30% by weight, it will become brittle and no practical composition can be obtained. The present invention provides a solution to these problems and relates to a relatively inexpensive thermoplastic elastomer and a tough polyamide-based thermoplastic resin composition obtained by adding this elastomer to a polyamide and polyolefin-based copolymer. Specifically, one is: A (1) an aliphatic α,ω-aminocarboxylic acid having a methylene chain of 10 or more carbon atoms or its lactam and/or an aliphatic diamine and at least one of the aliphatic dicarboxylic acids; It has a hard segment part made of a polyamide block containing at least one component of a diamine dicarboxylic acid salt with a methylene chain having 10 or more carbon atoms, and a soft segment part made of polyether and/or polyester. This is a thermoplastic polyamide elastomer composition obtained by kneading and reacting 10 to 90% by weight of a polyamide elastomer and (2) 90 to 10% by weight of a polyolefin resin in the presence of peroxide. The other is B (1) 5 to 50% by weight of the thermoplastic polyamide elastomer composition shown in A and (2) an aliphatic α,ω-aminocarboxylic acid having 10 or more carbon atoms in the methylene chain or A polyamide homopolymer obtained by polymerizing the lactam and/or a diamine dicarboxylate salt in which at least one of the aliphatic diamine and the aliphatic dicarboxylic acid has 10 or more carbon atoms in the methylene chain as at least one component; /or copolymer and (3) polyolefin copolymer resin (1)+(2)+(3)
40-95% by weight of polyamide component in the total composition of
This is a highly tough polyamide-based thermoplastic resin composition obtained by blending and melt-mixing to achieve the following properties. The thermoplastic polyamide elastomer composition obtained in A is a partially crosslinked modified elastomer obtained by melt-kneading a polyamide elastomer and a polyolefin resin in the presence of peroxide,
Although the raw material cost is reduced by adding the polyolefin resin, the properties as an elastomer are maintained because of the kneading reaction with the polyamide elastomer. In addition, the polyamide-based thermoplastic resin composition obtained in B can be obtained by blending a thermoplastic polyamide-based elastomer composition with a polyamide homopolymer and/or copolymer and a polyolefin-based copolymer resin as a compatibilizer. The polyolefin component inside is 30% by weight.
Even with the above composition, the resin composition still has strong physical properties. Next, the present invention will be explained in more detail. The polyamide elastomer described in A has a hard segment part made of a polyamide block and a soft segment part made of a polyether and/or polyester block, and is disclosed in JP-A-53-119997 and JP-A-52-12297. As can be seen, due to the ester bond, or
As shown in No. 133424, hard segment blocks and soft segment blocks are connected by amide bonds, and it is desirable that the polyamide blocks account for 40% by weight or more of the entire polyamide elastomer. Polyolefin resins used to modify polyamide elastomers include polypropylene, ethylene/propylene copolymer resins, polyethylene ionomers, ethylene, propylene rubber (EPDM), α-olefin/ethylene copolymers, etc. It will be done. That is, 90-10% by weight of the above polyolefin resin is blended with 10-90% by weight of polyamide elastomer, and 0.05% by weight is added to the weight of both.
~5% by weight, preferably 0.1~1% by weight of peroxide is added and melt-kneaded. If the polyamide elastomer is less than 10% by weight or more than 90% by weight in a blend of polyamide elastomer and polyolefin resin, the characteristics of the polyolefin resin or polyamide elastomer will be strong and the benefits of the blend will not be utilized. In addition, if the amount of peroxide added exceeds 5% by weight, the amount of radicals generated due to thermal decomposition of peroxide becomes too large, resulting in
In polyolefin resins containing units such as propylene with tertiary carbon atoms, molecular cleavage due to hydrogen abstraction attached to tertiary carbons is too large, and ethylene, propylene, etc., which have double bonds in the molecular chain, are
In polyolefin resins containing units such as rubber (EPDM) and ethylene without tertiary carbon, the crosslinking reaction proceeds too much and the properties of elastomers are lost. When the amount of peroxide added is less than 0.05% by weight, the amount of radicals generated from peroxide decreases, and the reaction between the polyamide elastomer and polyolefin resin becomes insufficient, causing so-called cold flow, and the elastomer cannot be used as an elastomer. The properties of the character become blurred. In general, it is preferable to add an amount of 0.1 to 1% by weight, but the optimum amount is small enough for polyolefin resins that have double bonds in their molecular chains because they are easily crosslinked due to the characteristics of the double bonds. It depends on the reactivity of the polyolefin resin used in combination with the elastomer. The peroxides used are dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-tert-butyl peroxy hexine, and 2,5-di-tert-butyl peroxide, which decompose at relatively high temperatures. Dimethyl, 2,5-di-tertiary, butyl, peroxy, hexane, etc. are suitable, and are melt-mixed with the polyamide elastomer and polyolefin resin using a Banbury mixer, co-kneader, twin-screw extruder, or the like. The thermoplastic polyamide-based elastomer composition obtained in this way has a use as an elastomer itself, but also has an action as a compatibilizer for polyamide and polyolefin-based copolymers. It has been discovered that a tough polyamide-based thermoplastic resin composition can be obtained by adding this thermoplastic polyamide-based elastomer composition to a polymer blend. That is, the polyamide homopolymer and/or copolymer described in (2) of Composition B is an aliphatic α-polymer having 10 or more carbon atoms in the methylene chain,
At least one of the ω-aminocarboxylic acid or its lactam and/or aliphatic diamine and aliphatic dicarboxylic acid has 10 carbon atoms in the methylene chain.
Polyamide homopolymer and/or copolymer obtained by polymerizing the above diamine dicarboxylate as at least one component, specifically nylon 10, nylon 11, nylon
12, homopolyamides such as nylon 610, nylon 612, nylon 1010, nylon 12/6, nylon 12/16/66, nylon 12/6/610, nylon
It refers to copolyamides such as 12/6/612, nylon 12/11/6/66, etc. alone or in mixtures.
In addition, the polyolefin copolymer resin shown in (3) of B is an olefin copolymer consisting mainly of ethylene and/or propylene, α-olefin such as butene-1, and specifically, ethylene-acetic acid. It means vinyl copolymer (EVA), ethylene/acrylate copolymer, ethylene/propylene copolymer, ethylene/α-olefin copolymer, ethylene/propylene diene monomer elastomer (EPDM), polyethylene ionomer, etc. A thermoplastic polyamide-based elastomer composition, that is, a polyolefin-modified polyamide elastomer, is added to the system consisting of the above-mentioned polyamide homopolymer and/or copolymer and polyolefin-based copolymer resin, but in this case, the polyamide component in the entire composition is It is necessary that the amount is 95% by weight. This is because if the polyamide component exceeds 95% by weight, the composition will not have any characteristics compared to polyamide itself, and if it exceeds 40% by weight, the properties of polyamide will be lost. Also, polyolefin-modified polyamide as a compatibilizer.
The elastomer is added in an amount ranging from 5 to 50% by weight, preferably from 10 to 30% by weight, based on the total composition. This is because if it is less than 5% by weight, the toughening effect is too low, and even if it is added in an amount of 50% by weight or more, no particularly noticeable effect has been observed. These are usually mixed by melt mixing. That is, polyamide
Homopolymer and/or copolymer pellets, polyolefin copolymer resin pellets, and polyolefin-modified polyamide elastomer pellets are mixed in a pellet form using a mixer such as a Henschel mixer or a tumbler mixer in proportions that satisfy the above conditions, In addition, kneading rolls and banbari
The final composition is obtained by melt-mixing using a kneading device such as a mixer, or more practically, by melt-mixing the mixed pellets using a co-kneader type extruder or twin-screw type extruder. Needless to say, various inorganic fillers such as talc, clay, mica, glass beads, glass fibers, and carbon fibers, various stabilizers for imparting weather resistance and heat resistance, and flexibility are added to this polyamide-based thermoplastic resin composition. It is possible to add additives such as a plasticizer for imparting, a lubricant for improving moldability, and other dyes and pigments and a fluorescent whitening agent as necessary, without impairing the above-mentioned effects. Next, specific applications of the present invention will be shown in Examples, but the content of the present invention is not limited to these Examples. Example 1 A material with a relative viscosity of 1.95 (0.5% m
- Melt flow index measured using 80 parts by weight of polyamide elastomer (hereinafter referred to as polyamide elastomer A) and polypropylene (190°C, 2160g, measurement conditions are the same below) at 25℃ of cresol solution: 10g/10min ) were mixed in the form of pellets, and then 0.5 parts by weight of dicumyl peroxide was made into a 10% acetone solution and uniformly dispersed in the mixed pellets using a Henschel mixer, followed by drying at 60°C for 3 hours. This mixed pellet is processed using a 30mmφ twin-screw extruder (rotating in different directions) at a cylinder temperature of 180℃ and a screw rotation speed of 33.3rpm.
Extruded polyolefin-modified polyamide elastomer pellets were obtained. Under these extrusion conditions, the residence time in the cylinder was approximately 9 minutes. The JIS Dampel test piece of the polyolefin-modified polyamide elastomer thus obtained had a tensile strength at break of 140 kg/cm ² and a tensile elongation at break of 340% (tensile speed
50 mm/min), and the compression set rate measured under the conditions of 70±1°C and 22°C was 53%. The above test method was based on JIS K6301-1975. In addition, in order to find out the degree of denaturation, a 1 mm thick press sheet was made, and a 25 mm x 25 mm x 1 mm test piece was heated at 120°C.
The degree of swelling in xylene was determined. At 120℃, equilibrium swelling is reached after about 3 hours of immersion, and the value is 510
It was %. The degree of swelling here is a value calculated by the following formula, and is a measure of the crosslinking reaction. Swelling degree = (weight after equilibrium swelling - weight before immersion) × 100 / (weight before immersion) For comparison, 80 parts by weight of polyamide elastomer A and 20 parts by weight of polypropylene were mixed in a tumbler mixer, and the same as before was mixed. Pellets were made under these conditions and their mechanical properties were measured. Its tensile strength at break was 127 kg/cm ² , its tensile elongation at break was 250%, and its compression set was 89%. Also, the degree of swelling is
It was partially dissolved in xylene at 120°C and could not be measured. That is, by carrying out a kneading reaction in the presence of peroxide, the properties of the thermoplastic polyamide elastomer composition are improved, and in particular, the rubber elastic properties are significantly improved as seen in the compression set rate. Example 2 Same as Example 1, nylon 12 component 74.2% by weight,
Polytetramethylene ether component 21.3% by weight,
Polyamide elastomer with a relative viscosity of 1.95 consisting of 4.5% by weight of decamethylene dicarboxylic acid (hereinafter referred to as polyamide elastomer B), nylon
12 components 43.0% by weight, polytetramethylene ether component 45.4% by weight, decamethylene dicarboxylic acid
A polyamide with a relative viscosity of 2.0 consisting of 11.6% by weight.
Elastomer (hereinafter referred to as polyamide elastomer C)
) and nylon 12 component 53% by weight molecular weight approx.
Relative viscosity consisting of 40% polyester component obtained from 400% polyethylene glycol and adipic acid and 7% decamethylene dicarboxylic acid.
1.8 polyamide elastomer (hereinafter referred to as polyamide elastomer D), peroxide-modified polyamide and polyolefin-based resins are produced.
I got an elastomer. Representative examples of these are shown in Table 1.

[Table] Example 3 Relative viscosity 2.10 (using 0.5% m-cresol solution)
Nylon 12 (measured at 25℃, measurement conditions are the same below)
Polyolefin modified in Example 1 was added to 50% by weight of homopolymer pellets and 30% by weight of pellets of ethylene-propylene elastomer (marked rubber: Bestpren TP2037, melt flow index: 0.8g/10min, manufactured by Huls AG, West Germany). 20% by weight of polyamide elastomer pellets were mixed using a tumbler mixer, and then melt mixed and pelletized using a 30 mmφ twin screw extruder (rotating in different directions) at a cylinder temperature of 220°C and a screw rotation speed of 80 rpm. The tensile properties of this polyamide-based thermoplastic resin composition using a dumbbell test piece were determined at a tensile rate of 50 mm/min.
The tensile strength at break was 253 kg/cm ² and the tensile elongation at break was 310%. On the other hand, for comparison, 60% by weight of nylon 12 homopolymer pellets with a relative viscosity of 2.10 and the same ethylene-propylene elastomer pellets as in the above example were used.
40% by weight (60% by weight as 12 nylon components)
were melt-mixed under the same conditions, and the tensile properties of the resulting composition were measured in the same manner, and a tensile strength at break of 159 kg/cm ² and a tensile elongation at break of 100% were obtained. Similarly, a composition containing 70% by weight of nylon 12 homopolymer pellets and 30% by weight of ethylene/propylene elastomer has tensile strength at break.
202kg/cm ² , tensile elongation at break 85%, and nylon
A composition containing 50% by weight of 12 homopolymer pellets and 50% by weight of ethylene propylene elastomer had a tensile strength at break of 100 kg/cm ² and a tensile elongation at break of 45%. The toughness of the composition is improved by adding a polyolefin-modified polyamide elastomer as a compatibilizer. Example 4 The relative viscosity was determined using various polyolefin-modified polyamide elastomers obtained in Example 2 as a compatibilizer.
In addition to the mixed pellets of nylon 12 homopolymer pellets and polyolefin copolymer resin pellets of 2.10, the mixture was melt-mixed at 220°C in a twin-screw extruder in the same manner as in Example 3 to obtain a composition. These results are shown in Table 2. The compositions obtained according to the present invention were flexible and tough in all cases. Note that Table 2 also includes comparative experimental examples for reference.

【table】

Claims (1)

[Scope of Claims] 1 (1) At least one of an aliphatic α,β-aminocarboxylic acid or its lactam and/or an aliphatic diamine and an aliphatic dicarboxylic acid having a methylene chain having 10 or more carbon atoms. A hard segment part made of a polyamide block containing as at least one component a salt of diamine dicarboxylic acid whose methylene chain has 10 or more carbon atoms, and a soft segment part made of polyether and/or polyester. An elastic thermoplastic polyamide composition obtained by kneading and reacting 10 to 90% by weight of a polyamide elastomer having (2) 90 to 10% by weight of a polyolefin resin in the presence of a peroxide. 2 (1) At least one carbon in the methylene chain of an aliphatic α,ω-aminocarboxylic acid or its lactam and/or an aliphatic diamine and an aliphatic dicarboxylic acid having 10 or more carbon atoms in the methylene chain A polyamide elastomer having a hard segment part made of a polyamide block containing at least one component of a diamine dicarboxylic acid salt having 10 or more atoms, and a soft segment part made of polyether and/or polyester. Tomer 10-90% by weight and polyolefin resin 90%
Thermoplastic polyamide composition 5 obtained by kneading and reacting with ~10% by weight in the presence of peroxide
50% by weight and (2) an aliphatic α,ω-amino carboxylic acid or its lactam with a methylene chain having 10 or more carbon atoms and/or an aliphatic diamine and an aliphatic dicarboxylic acid in which at least one has a methylene chain. (1) a polyamide homopolymer and/or copolymer obtained by polymerizing a diamine dicarboxylate having at least 10 carbon atoms as at least one component; and (3) a polyolefin copolymer resin. +(2)+(3)
A highly tough thermoplastic polyamide composition obtained by blending and melt-mixing so that the polyamide component in the total composition is 40 to 95% by weight.