JPS6164747A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having excellent rubber elasticity, mechanical characteristics and moldability, by blending a polystyrene block copolymer with a polyether ester amide. CONSTITUTION:99-1pt.wt. polystyrene block copolymer is blended with 1-99pts. wt. polyether ester amide derived from a 6C or higher aminocarboxylic acid or lactam or a salt of a dicarboxylic acid with a 6C or higher diamine (a), a poly(alkylene oxide) glycol (b) having a number-average MW of 300-6,000 and a 4-20C dicarboxylic acid (c). As component (a), 11-aminoundecanoic and 12-aminododecanoic acids are particularly preferred. As the glycol (b), poly (tetramethylene oxide) glycol is preferred from the viewpoints of resistance to heat and water, mechanical strength, elastic recovery and excellent physical properties inherent to the polyether ester amide.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field for FIJ> The present invention relates to a polyether ester amide resin composition having excellent rubber elasticity, mechanical properties, and moldability.

<Prior art> Polyether ester amide having a polyamide repeating unit, a polyether repeat unit, and an ester bond in the main polymer = 'L1 is well known, and has excellent impact resistance and rubber elasticity like polyether ester or polyester amide. Because of this, it is attracting attention as a new material in the elastomer field.

<Problems with conventional technology> Polyether ester amide is lightweight, has excellent low-temperature impact resistance, and is less likely to cause flakes or sink marks during molding.
Although it is promising for various molding applications, it has the disadvantage of being inferior in flexibility compared to rubber. Production of polyetheresteramide with a hardness comparable to that of rubber can be achieved by increasing the number of layers containing soft components, but this tends to result in lower melting points, high-temperature properties, and moldability.

On the other hand, polystyrene-type block co-assemblies exhibit excellent properties such as rubber elasticity and low-temperature properties, but suffer from the disadvantage of being inferior in mechanical strength and heat resistance. Moreover, in particular, during injection molding, the adhesiveness during tg melting is strong, resulting in poor mold releasability from the mold, long molding cycle time, and low productivity.

The present inventors conducted intensive studies to solve the above-mentioned drawbacks of polyether ester amide, and as a result, they discovered the present invention.

The present inventors have discovered that a blend of polystyrene-type block copolymer with polyether ester amide retains the excellent features of polyether ester amide, while significantly improving flexibility and properties, which are its drawbacks. I found it.

Means for Solving the Problems> That is, the present invention provides a salt (a) of an aminocarbo/acid or lactam having 6 or more carbon atoms or a dicarboxylic acid with a diamine having 6 or more carbon atoms,! A polyether ester amide (2) derived from a poly(alkylene/oxide) glycol (b) having an average molecular weight of 300 to 6000 and a dicarbonate U (C) having 4 to 20 carbon atoms. This is a resin composition containing 99 to 1 part by weight of copolymer (1).

In the present invention, the salt (a) of an aminocarboxylic acid or lactam having 6 or more carbon atoms or a diamine and dicarboxylic acid having 6 or more carbon atoms includes ω-amitsukagulonic acid, ω-
Aminocarboxylic acids such as amine ditentic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminecapric acid, It-aminoundecane tQ, 12-aminododecanoic acid, or caprolactam, enantholactam, caprylic dicutam, lauro Lactams such as lactams and diamine dicarboxylic acids such as hexamethylenediamine-sepanoate and hexamethylenediamine-isophthalate;
There are salts of acids, especially ll-amitsu/decanoic acid, 12
-Aminododecanoic acid is preferred, and these can be used in combination depending on the purpose and use.

Further, it is also permissible to use other amide-forming components as copolymerization components for the purpose of lowering the melting point of polyether ester amide or increasing adhesiveness, as long as the mJ range is small.

The poly(alkylene/oxide) glycol (b) having a number average molecular weight of 300 to 6.000 in the present invention includes:
Polyethylene glycol, poly (112- and 1.
Examples include 3-propylene oxide) glycol, poly (tetramethylene oxotogelicol), poly (hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, etc. Among them, poly(tetramethylene oquinodo) glycol is preferably used because of the excellent physical properties of polyether ester amide, such as heat resistance, water resistance, mechanical strength, and elastic recovery. The number average molecular weight of poly(alkylene oxide) glycol is 300 to 6,0
Although it can be used within the range of Poly
(Alkylene oxide) Varies depending on the type of glycol.

For example, in the case of polyethylene glycol, 300 to 6,000
0, particularly preferably 1,000 to 4,000, is poly(
For propylene oquinide) glycol 300~s, o
oo, particularly preferably from 500 to 3,000, and in the case of poly(tetramethylene oxide) glycol, 500
~3,000. Particularly preferably, those in the molecular weight range of 500 to 2,500 are preferably used.

In the present invention, dicarboxylic acids (C) having 4 to 20 carbon atoms include terephthalic acid, isophthalic acid, naphthalene-2,
6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid 1
Diphenyl-4,4'-dicarboxylic acid, Difenoquinethanedicarboxylic acid, Sodium 3-sulfoinophthalate, aromatic dicarboxylic acid/m, 1,4-Cyclohexa/dicarboxylic acid, 1,2-Fuclohexa/ dicarboxylic acids, dicarboxylic acids such as di/chlorohexyl//l/-4,4'-dicarboxylic acids;
Mention may be made of aliphatic dicarboxylic acids such as d1 acid, adipic acid, sebanyl acid, and dodecanedioic acid (deca/dicarboxylic acid). In particular, dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-chlorohexa7 dicarboxylic acid, sepanonic acid, and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone, and physical properties of the polymer.

The present invention provides a salt (a) of the above-mentioned aminocarboxylic acid or lactam or diamine having 6 or more carbon atoms and dicarboxylic acid.
, poly(alkylene/oquinodo)glycol having a number average molecular weight of 1,300 to 6,000) and a dicarboxylic acid (C) having 4 to 20 carbon atoms. Polystyrene type block 8 body 0? It is a resin composition formed by blending. The relative viscosity of the polyether ester amide used in the present invention is preferably in the range of 1.2 to 3.5, particularly L5 to 2.0.
A range of is preferred.

The polystyrene type block copolymer used in the present invention is
It is a block copolymer consisting of a high melting point polystyrene block and a rubber phase block. The high melting point polystyrene block is a polymer of styrene or a derivative thereof having a glass transition temperature of 25° C. or higher, preferably 50° C. or higher, such as polystyrene, polymethylstyrene, polychlorostyrene 7, etc. Further, the rubber phase block is a polymer having a glass transition temperature of 0°C or lower, preferably -25°C or lower, such as polybutadiene,
Polyisoprene, polymethyl inofre/etc. There are many combinations of high melting point polystyrene blocks and rubber phase blocks, and any of them may be used, but a block copolymer with a rubber phase block bonded in the middle is preferred.

The proportion of the high melting point polystyrene block in the polystyrene type block copolymer is preferably 10 to 50% by weight, and the proportion of the rubber phase block is preferably 90 to 50% by weight.

The polystyrene type block copolymer can be produced using the known sliding anio-7 polymerization method, but is not particularly limited thereto, and can also be produced by cationic polymerization or radical polymerization.

The method for polymerizing the polyether ester amide prisoner is not particularly limited, and any known method can be used. For example, by reacting an aminocarboxylic acid or a lactam or a diamine with a dicarboxylic acid salt (a) and a dicarboxylic acid (C), a polyamide prepolymer having carboxy acid groups at both ends is formed (poly(alkylene ochind) is formed into a polyamide prepolymer having carboxy acid groups at both ends). Glycol (
b) A method of reacting under vacuum, or the above (a),
The compounds (b) and (C) are charged into a reaction tank and reacted by heating at high temperature in the presence or absence of water to produce a carboxy/acid-terminated polyamide prepolymer. It is known how to proceed with the conjunction below.

There is also a method in which the compounds (a), (b), and (C) above are simultaneously charged into a reaction tank, melted and centered, and then polymerized all at once under high vacuum. Less is preferable.

In the present invention, the blending ratio of polyether ester amide ^ and polystyrene type block copolymer (2) is such that the polystyrene type block co-electropolymer @ 99 to IM parts is mixed with 1 to 99 parts by weight of polyether ester amide. Particularly preferably, the amount of the polystyrene type block coelectrolyte is 50 to 5 parts by weight per 50 to 95 parts by weight of the polyether ester amide (2).

If the blending ratio of the polystyrene-type block copolymer (2) is less than 1 part by weight, no effect of its blending will be exhibited at all.

Furthermore, if the blending ratio of the polystyrene type block copolymer (c) is greater than 99 parts by weight, the features of polyether ester amide will be completely lost.

Of course, the physical properties of the resin composition of the present invention are also influenced by the composition of the polyether-steramide (2), but the proportion of poly(alkylene oquinodo) glycol in the polyether esteramide is 5-90
Heavy soaking percentage is desirable.

The resin composition of the present invention is preferably melted and kneaded by itself, and a known method can be used for melting and kneading. For example, the resin composition can be prepared by melt-kneading using a Banbury mixer, a Combroll machine, a screw-screw or twin-screw extruder, etc., usually at a temperature of 100 to 250°C.

The resin composition of the present invention also contains known antioxidants, thermal decomposition inhibitors, violet ray absorbers, hydrolysis resistance;
C! ! , agent (face + 4S dye), antistatic agent, special agent,
Yuenkan, reinforcing agent, filler, in 7'lJ, nucleating agent, kJ
A molding agent, plasticizer, adhesion aid, adhesive, etc. can be optionally contained.

The present invention will be explained below with reference to Examples. In the examples, unless otherwise specified, parts mean parts by weight.

<Example> .

Reference Example Polymerization of polyether ester amide (A-1) 9 parts of ω-aminododeca 7Fm8L, 5.3 parts of terephthalic acid, and 20.8 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 650 were mixed into 1 Irganox'' 109
8 Pour 0.5 parts (antioxidant) into a reaction vessel equipped with a helical ribbon stirring blade, purge with nitrogen, and heat to 260°C.
Heat and stir for 1 hour to obtain a homogeneous transparent film! After making it into a solution,
Antimore dioxide catalyst (), 0.015 parts, monobutyl monohydroxide, tokoxytin oxide catalyst 0.015 parts, phosphoric acid 0.015 parts.
0.005 parts (anti-coloring agent) was added and a vacuum program was followed to bring about polymerization conditions of less than 1 x mHy in 1 hour. When the reaction was carried out under these conditions for 2.5 hours, a viscous colorless and transparent molten polymer was obtained, and when this polymer was discharged into water as a gut, it crystallized and turned white. The obtained polyether ester amide (A-1) had a relative viscosity (ηr) of 181 when measured in orthochromitzenol at 25°C and a 0.5 part strength test, and a crystal melting point of 167°C by DSC. Met.

Polymerization of polyether ester amide (A-2) 49.1 parts of ω-aminododecane m, 7.9 parts of terephthalate, 4 & 8 parts of poly(tetramethylene oxide) glycol having a mean molecular weight of 1020, 6-irganox”1098
15 parts, antimony trioxide 0.015 parts, monobutyl monohydroxytin oxide 0.015 parts, and phosphoric acid o,
i = from the oos part under the same conditions as polymer (A-1)
A polyether ester amide (A-2) having a relative viscosity of L93 and a melting point of 154°C was obtained.

Polymerization of polyether ester amide (A-3) 27.3 parts of ω-aminododecane, 567 parts of terephthalic acid, poly(tetramethylene oxide) with a ridge average molecular weight of 2060
Glycol 70.5 parts, "Irganox" 1098
0.5 part of antimony trioxide, ors part, 0.015 part of motuputyl monohydroxytin oxide, and phosphoric acid o, oos part were weighted in the same order as polymer (A-1), and the relative viscosity αL92 , a polyether ester amide (A-3) having a melting point of 145''C was obtained.

Polymerization of polyether ester amide (A-4): 449 parts of methylene diamine-azibi/acid acid, 12.8 parts of terephthal, poly(tetramethylene oxide) glycol 5O-O with a number average molecular λ of 650. Part, 1 Irganox” 10980.5 parts, 3 parts, 7 parts, 0.01
5 parts, monobutyl monohydroxytin oxide 0.015
part, and phosphoric acid o, ooszt to polymer (A-■)
Polymerized under the same conditions as , relative viscosity L80, melting point 209℃
A polyether ester amide (A-4) was obtained.

Examples 1 to 9 Styrene-butadiene pronoc copolymer (
Two units of styrene-isoprene block copolymer (hereinafter referred to as 5IS) or styrene-isoprene block copolymer (hereinafter referred to as 5IS) were installed. Commercially available products can be used for polystyrene block combinations,
In this example, Aron Kasei AR-480 was used as the SBS.
Aron Kasei AR-800 was used as StS.

First, to the polyether ester amide formula polymerized according to the above reference example, SBS or SIS was incorporated with ffi at the ratio shown in Table 1, and in the case of SBS, at 200 ° C.
In the case of SIS, it was melt-kneaded at 220°C and pelletized. The resulting pellets are then heated to 200 °C in the case of SBS using an injection molding machine with an injection capacity of 5 oz.
In the case of SIS, JIS No. 2 tensile test pieces were molded at a temperature of 220°C and a mold temperature of 80°C. Tensile properties and hardness meet ASTM D-638 and ASTIVI D-2, respectively.
Measured according to 240.

Effects of the present invention> As is clear from the hardness values shown in Table I, by blending SBS or SIS with polyetheresteramide, the hardness decreases significantly and the flexibility of polyetheresteramide decreases. Significant improvement.

Claims (1)

[Claims] Aminocarboxylic acid or lactam having 6 or more carbon atoms or salt of diamine and dicarboxylic acid having 6 or more carbon atoms (a),
Polyether ester amide (A) derived from poly(alkylene oxide) glycol (b) having a number average molecular weight of 300 to 6000 and dicarboxylic acid having 4 to 20 carbon atoms
1 to 99 parts by weight of polystyrene block copolymer (
A resin composition containing B) in a proportion of 99 to 1 part by weight.