JPS6142565A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. which has a high viscosity and gives moldings having excellent mechanical properties by extrusion or blow molding, consisting of a polyether esteramide and an olefin copolymer. CONSTITUTION:A polyether esteramide composed of 6C or higher aminocarboxylic acid (e.g. 11-aminoundecanoic acid), lactam or a salt of 6C or higher diamine and dicarboxylic acid (a), a poly(alkylene oxide)glycol (b) having a number-average MW of 300-6,000 and a 4-20C dicarboxylic acid (c) (e.g. terephthalic acid), and an olefin copolymer composed of alpha-olefin (x) (e.g. ethylene) and a glycidyl ester of an alpha,beta-unsaturated acid (y) (e.g. glycidyl methacrylate), are used. 50-99wt% said polyether esteramide is melt-kneaded with 50-1wt% said olefin copolymer at 100-300 deg.C.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention has a high viscosity and excellent mechanical properties.
The present invention relates to a Δfat composition.

<Prior art> Polyetheresteramides having polyamide repeating units, polyether repeating units, and ester bonds in the polymer main chain are well known, and have excellent impact resistance and rubber elasticity like polyetheresters or polyesteramides. Therefore, it has attracted attention in recent years as a new material in the elastomer field.

In particular, polyether ester amide is promising for injection molding applications because it has excellent lightness and transparency, and is less likely to cause flakes, sink marks, etc. during molding.

It is also more flexible than polyamide resin and has excellent impact resistance at room and low temperatures.

Although polyether ester amide has the above-mentioned characteristics, it has problems such as being easily colored and having poor elastic recovery properties, and improvements are desired. For example, high viscosity is necessary to manufacture tubes, bellows, etc. by extrusion molding or blow molding, but if the texture time is extended to obtain high viscosity, coloration tends to become worse. Furthermore, polyether ester amide has a relatively low melting point, making it difficult to perform in-phase polymerization, which necessitates liquid phase polymerization, which has the problem of increasing coloration.

<Problems to be Solved by the Invention> The present invention solves the above-mentioned problems and provides a 6u product with high viscosity and excellent
The object of the present invention is to provide a polyetheresteramide resin composition having CA properties.

Means for Solving the Problems> The above-mentioned problems of the present invention can be solved by using an aminocarboxylic acid or a lactam having 6 or more carbon atoms, or a diamine and dicarboxylic acid salt (a) having a number average molecular weight of 300 or more. ~6
,000 poly(alkylene oxide) glycol Φ)
, and polyether ester amide (c) 50-9 composed of dicarboxylic acid (c) having 4 to 20 carbon atoms
This can be achieved by making a resin composition consisting of 9% by weight and 050-1% by weight of an olefin copolymer consisting of α-olefin (2) and glycidyl ester of α,β-unsaturated acid (y). .

Aminocarboxylic acid or lactam having 6 or more carbon atoms or diamine having 6 or more carbon atoms in the polyether ester amide (3) of the present invention
a) - refers to amino acids such as ω-7 minocaproic acid, ω-amine enanthate, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-amine capric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc. Carboxylic acids or lactams such as caprolactam, enantholactam, capryllactam, laurolactam, and hexamethylenediamine adipate, hexamethylenediamine
Sebacate, Hexamethylenediamine-Isophthalate, Undecamethylenediamine-Adipate, 4.4
There are salts of diamine-dicarboxylic acids such as '-diaminodicyclohexylmecundodecanedate, especially 11
-aminoundecanoic acid, 12-amino.

Dodecanoic acid is preferred, and these may be used in combination depending on the purpose and use.

It is also permissible to use other amide-forming components as copolymerization components in small amounts for the purpose of lowering the melting point of polyether ester amide or increasing adhesiveness.

The poly(alkylene oxide) glycols having a number average molecular weight of 300 to 6,000 in the polyether ester amide (2) of the present invention include polyethylene glycol, poly(1,2- and 1,3-propylene oxide) glycol , poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, among others, which have excellent heat resistance and water resistance. Poly(tetramethylene oxide) glycol is preferably used to obtain the excellent physical properties of polyether ester amide, such as elasticity, mechanical strength, and elastic recovery. The number average molecular weight of poly(fulkylene oxide) glycol is 300 to 6,000
However, during polymerization, a molecular weight range that does not cause coarse phase separation and has excellent low-temperature properties and mechanical properties is selected, and this optimum molecular weight range differs depending on the type of poly(alkylene oxide) glycol. .

For example, in the case of polyethylene glycol, it is 300 to 6.00
0, particularly preferably 1,000 to 4,000,
(propylene oxide) glycol 300-5,
000, particularly preferably from 500 to 3,000, and in the case of poly(tetramethylene oxide) glycol, 50
0-3,000. Particularly preferably 500 to 2,50
Those in the molecular weight range of 0 are preferably used.

Examples of the dicarboxylic acid (c) having 4 to 20 carbon atoms in the polyether ester amide (6) of the present invention include terephthalic acid, isophthalic acid, naphthalene-2゜6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4 ，
Aromatic dicarboxylic acids such as 4'-dicarboxylic acid, diphenoxyethane dicarboxylic acid, sodium 3-sulfoisophthalate, l,4-cyclohexane dicarboxylic acid, 1
．． Aliphatic dicarboxylic acids such as 2-cyclohexanedicarboxylic acid, synchronohexyl-4,4'-dicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, pyroic acid, adipic acid, sepacic acid, dodecanedioic acid (te'canedicarboxylic acid) Mention may be made of dicarboxylic acids. In particular, dicarboxylic acids such as terephthalic acid, isophthalic P,1,4-cyclohexanedicarboxylic acid, sebanic acid, and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone, and physical properties of the polymer.

In order for the effect of the present invention to be particularly evident in the middle stage, the amount of copolymerization of poly(alkylene oxide) glycol (b) in the polyether ester amide formula is preferably 5 to 90%. If the copolymerization amount is less than 5 MQ%, flexibility and elastic recovery properties will be lost, whereas if it exceeds 90% by weight, high-temperature properties,
Mechanical strength is not sufficient.

The method for polymerizing polyether ester amide (1) is not limited to the conventional method, and any known method can be used. For example, aminocarboxylic acids or lactams (a) and dicarboxylic [f
i (c) to produce a polyamide prepolymer having carboxylic acid groups at both ends, and reacting this with poly(alkylene oxide) glycol (b) under vacuum, or the above (a), (b), ( There is a method in which the compound c) is charged into a reaction tank and heated to react at high temperature in the presence or absence of water to produce a carboxylic acid-terminated polyamide prepolymer, and then polymerization is proceeded under normal pressure or reduced pressure. Are known.

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

The olefinic copolymer consisting of α-olefin (3) and α,β-unsaturated acid glycidyl nitrate used in the present invention is a copolymer containing at least two components (2) and (2). , α-olefin ((trans)) here is
Examples include ethylene, propyleno, butene-1, and ethylene is preferably used. Also, it is a compound represented by α,β-unsaturated acid glycidyl varnish (in the formula, R is a hydrogen atom or a lower alkyl group), specifically glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate. etc., and glycidyl methacrylate is preferably used. The copolymerized amount of the glycidyl ester q) of an α,β-unsaturated acid in the olefin copolymer is suitably in the range of 0.1 to 50 mol%, preferably 0.5 to 5 mol%. Furthermore, unsaturated monomers that can be copolymerized with the above copolymer if 40 mol% or less, preferably 30 mol% or less (in this case, the total of three or more copolymerized components will be 100 mol%), Vinyl ethers, vinyl esters such as vinyl acetate and vinyl propionate, esters of acrylic acid and meccrylic acid such as methyl, ethyl, and propyl, acrylonitrile,
Styrene or the like may be copolymerized. Among them, vinyl acetate is preferably used.

In the present invention, the blending ratio of polyether ester amide (c) and olefin copolymer 0 must be such that (1) is 50 to 99% by weight and (2) is 50 to 1% by weight.

If (c) is less than 1% by weight, the thickening effect of the present invention is small;
Moreover, if it exceeds 50% by weight, the excellent mechanical properties of the polyether ester amide will be impaired, which is not preferable.

The resin composition of the present invention is preferably melt-kneaded, and a known method can be used for the melt-kneading method. For example, the resin composition can be prepared by melt-kneading the resin composition using a Banbury mixer, a rubber roll machine, a screw-screw or twin-screw extruder, etc., usually at a temperature of 100 to 300°C.

The resin composition of the present invention also contains known antioxidants, thermal decomposition inhibitors, ultraviolet absorbers, hydrolysis resistance improvers, colorants (
Pigments, dyes), antistatic agents, conductive agents, fuel agents, reinforcing agents, fillers, lubricants, nucleating agents, type agents, adhesion aids, adhesives, etc. can be optionally contained.

Further, the composition of the present invention can be used as a composite material having excellent mechanical properties, especially impact resilience, by breading ionomer II nW in applications requiring such properties.

The ionomer resin here refers to α-olefin and α,
It is a copolymer of β-unsaturated carboxylic acid salt, and is an ionic copolymer containing mono- to trivalent metal ions.

<Effects of the Invention> According to the present invention, a high viscosity composition can be obtained while retaining the excellent mechanical properties of polyether ester amide (5), and can be made into tubes, dust covers, bellows, etc. by extrusion molding or blow molding. Suitable for molding various shapes such as boots.

<Examples> Unless otherwise specified in the examples, the number of copies means fffffl copies.

Reference Example Polymerization of Polymer (A-1) 819 parts of ω-aminododecanoic acid, 6.8 parts of dodecanedioic acid and 19.3 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of 650 were added to 1 Irganox'.
10,98 with 0.5 part (antioxidant) in a reaction vessel equipped with a helical ribbon stirring system, purged with N2, heated and stirred at 260°C for 1 hour to obtain a homogeneous transparent solution,
Antimony dioxide catalyst 0.015i, monobutyl monohydroxytin oxide catalyst 0.015 parts, phosphoric acid 0.0
05 parts (anticolor agent) were added and a vacuum program was followed for 1 hour to bring the polymerization conditions to <1jffHf.

When reacted 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 orthochlorophenol at 25°C at a concentration of 0.5%, and a crystal melting point of 167°C by DSC.

Polymerization of Polymer (A-2) 1149.1 parts of ω-aminododecane, 7.0 parts of terephthalic acid.
9 parts, 48.8 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 1020, 'Irganox'
10980.5 parts of antimony dioxide, 15 parts of antimony dioxide, 0.015 parts of monobutyl monohydroxytin oxide, and 0.005 parts of phosphoric acid under the same conditions as for polymer (A-1) to obtain a relative viscosity of 193 and m point. A polyether ester amide (A-2) having a temperature of 154°C was obtained.

Polymerization of polymer (A-3) 27.3 parts of ω-aminododecanoic acid, 5.7 parts of terephthalic acid
70.5 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of 2060, t Irganox '1
0,980.5 parts of antimony trioxide, 0.015 parts of antimony trioxide, 0.015 parts of monobutyl monohydroxytin oxide, and 0.005 parts of phosphorus fi under the same conditions as Polymer (A-1), with a relative viscosity of 192 and a melting point of A polyether ester amide (A-3) having a temperature of 145°C was obtained.

44.9 parts of polymerized undecamethylenediamine-adipate of polymer (A-4),
12.8 parts of terephthalic acid, 50.0 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of 650,
'Irganox' 1098o, si, 0.015 part of antimony trioxide, 0.015 part of monobutyl monohydroxytin oxide, and 0.005 part of phosphoric acid were polymerized under the same conditions as for polymer (A-1), and the relative Viscosity L8
0, polyether ester amide (A
-4) was obtained.

The copolymer composition and abbreviation of olefin copolymer ① used in the olefin copolymer examples are as follows.

Examples 1 to 10, Comparative Example 3 (Comparative Example 12 will be described later) Polyetheresteramide block copolymer (A-1), (
A-2), (A-3) and (A-4) are mixed with the olefin copolymer shown in the table and, in some cases, an ionomer resin, to form (A-1), (A-2) and (A-4). 3) was melted and kneaded in a 3 Q myφ extruder heated to 200°C, and (A-4) to 240°C, and then pelletized. The obtained pellets were heated at 200°C for (A-1), (A-2) and (A-3), and at 240°C for (A-4) using an injection molding machine with an injection capacity of 50Z. And, the mold temperature is 40℃ and J'I52
A No. 1 tensile test piece was molded.

Tensile properties are ASTm D-6,38 and hardness is AS
T4VI D-2240, melting index is ASTM D-
1238. The results are shown in the table.

Comparative Example 1, 2.4.5 Polyether ester amide (A-1), (A-2),
Examples 1 to 1O1 for (A-3) and (A-4)
Tensile properties, hardness, and melting index were measured in the same manner as in Comparative Example 3. The results are shown in the table.

As seen in Examples 1 to 11, it can be seen that the resin compositions of the present invention have decreased melting index and increased viscosity while maintaining the excellent mechanical properties of polyether ester amide.

Claims (1)

[Claims] Aminocarboxylic acids or lactams having 6 or more carbon atoms,
Or a salt of diamine and dicarboxylic acid having 6 or more carbon atoms (
a), poly(alkylene oxide) glycol (b) having a number average molecular weight of 300 to 6,000, and having 4 carbon atoms
50 to 99% by weight of a polyether ester amide (A) composed of ~20 dicarboxylic acids (c), and an olefin system composed of an α-olefin (x) and a glycidyl ester of an α,β-unsaturated acid (y) A resin composition comprising 50 to 1% by weight of a copolymer (B).