JPH0521150B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention has high crystallinity, high melt viscosity, moldability,
This invention relates to a polyetheresteramide resin composition with excellent mechanical properties. <Prior Art> Polyetheresteramides having polyamide repeating units, polyether repeating units and ester bonds in the polymer main chain are known (US Pat. No. 3,044,987). <Problems to be solved by the invention> Polyether ester amide is useful for various molding applications because it is lightweight, has excellent elastic recovery properties, transparency, and low-temperature impact resistance, and is less likely to cause burrs, sink marks, etc. during molding. However, since the crystallization rate and the achieved crystallinity are low, in the case of melt molding, a relatively long cooling time is required, resulting in a decrease in productivity. In addition, high viscosity is necessary for manufacturing tubes, bellows, etc. by extrusion molding or blow molding, but if the polymerization time is extended to obtain high viscosity, coloring tends to become severe. In addition, polyether ester amide has a relatively low melting point and is difficult to perform solid phase polymerization, so liquid phase polymerization has to be performed, which has the problem of increasing coloration. The present invention has been made to solve the above-mentioned problems and to provide a resin composition that has high crystallinity, high melt viscosity, and excellent moldability and mechanical properties. <Means for Solving the Problems> As a result, the above object of the present invention is achieved when the number of carbon atoms is 6.
The above aminocarboxylic acids or lactams, or salts of diamines and dicarboxylic acids having 6 or more carbon atoms
(a), poly(alkylene oxide) glycol (b) having a number average molecular weight of 300 to 6000, and a number of carbon atoms of 4 to
Polyether ester amide (A) composed of 20 dicarboxylic acids (c) with 4 to 99 parts by weight of carbon atoms
9 aminocarboxylic acid or lactam (d) and/or
Or, it can be achieved by mixing 50 to 1 part by weight of a polyamide (B) composed of a diamine having 4 to 9 carbon atoms and a dicarboxylic acid salt (e) to form a polyether ester amide composition. I found out that. The structure, embodiments, and effects of the present invention will be described below. Examples of the aminocarboxylic acid or lactam having 6 or more carbon atoms or the diamine and dicarboxylic acid salt (a) having 6 or more carbon atoms in the polyether ester amide (A) of the present invention include ω-aminocaproic acid, ω
-aminoenanthic acid, ω-aminocaprylic acid, ω
-aminopelargonic acid, ω-aminocapric acid,
Aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid or caprolactam,
Lactams such as enantlactam, capryllactam, laurolactam and hexamethylenediamine-adipate, hexamethylenediamine-sebacate, hexamethylenediamine-isophthalate, undecamethylenediamine-adipate, 4,4'- Diaminodicyclohexylmethane
There are salts of diamine-dicarboxylic acids such as dodecanedioic acid salts, especially 11-aminoundecanoic acid, 12-
Aminododecanoic 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. Examples of the poly(alkylene oxide) glycol (b) having a number average molecular weight of 300 to 6,000 in the polyether ester amide (A) 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, etc., among others, have excellent heat resistance and water resistance. Poly(tetramethylene oxide) glycol is preferably used because of the excellent physical properties of polyether ester amide, such as mechanical strength, elastic recovery, etc. The number average molecular weight of poly(alkylene oxide) glycol is 300~
6000, but a molecular weight range that does not cause coarse phase separation during polymerization and has excellent low-temperature properties and mechanical properties is selected, and this optimum molecular weight range varies depending on the type of poly(alkylene oxide) glycol. . For example, in the case of polyethylene glycol, it is 300~
6000, particularly preferably 1000-4000, 300-5000 in the case of poly(propylene oxide) glycol,
Particularly preferably 500 to 3000, and in the case of poly(tetramethylene oxide) glycol, 500 to 3000;
Particularly preferably, those in the molecular weight range of 500 to 2,500 are preferably used. Examples of the dicarboxylic acid (c) having 4 to 20 carbon atoms in the polyether ester amide (A) of the present invention include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid,
Aromatic dicarboxylic acids such as diphenyl-4,4'-dicarboxylic acid, diphenoxyethane dicarboxylic acid, sodium 3-sulfoisophthalate, 1,4
-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,
Alicyclic dicarboxylic acids such as 4'-dicarboxylic acids,
and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedioic acid (decanedicarboxylic acid).
In particular, dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone, and physical properties of the polymer. In order for the effects of the present invention to be exhibited most significantly, the copolymerization amount of poly(alkylene oxide) glycol (b) in polyether ester amide (A) is preferably 5 to 90% by weight. Copolymerization amount is 5% by weight
If it is less than 90% by weight, flexibility and elastic recovery properties will be lost, and if it is more than 90% by weight, high temperature properties and mechanical properties will not be sufficient. The method for polymerizing polyether ester amide (A) is not particularly limited, and any known method can be used. For example, aminocarboxylic acids or lactams
A method of reacting (a) with dicarboxylic acid (c) to create a polyamide prepolymer having carboxylic acid groups at both ends, and reacting this with poly(alkylene oxide) glycol (b) under vacuum, or (a) above, 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 carboxylic acid-terminated polyamide prepolymer, and then heated under normal pressure or reduced pressure. Methods of advancing polymerization are known. There is also a method in which the compounds (a), (b), and (c) above are charged into a reaction tank at the same time, melt-polymerized, and then polymerized all at once under high vacuum; this method actually causes less coloring of the polymer. preferable. The polyamide (B) composed of an aminocarboxylic acid or lactam having 4 to 9 carbon atoms or a lactam (d) and/or a salt of a diamine and dicarboxylic acid having 4 to 9 carbon atoms (e) of the present invention includes nylon 6, nylon 46,
nylon 49, nylon 66, nylon 69, nylon
6I (polyhexamethylene isophthalamide), nylon 6T (polyhexamethylene terephthalamide)
Homopolyamides such as nylon 6/66, nylon 46/66, nylon 6/6T, nylon 6/
Copolyamides such as 6I, nylon 66/6T, nylon 66/6I, nylon 6/66/6T, nylon 6/66/6I (slush means copolymer in the above) and mixtures thereof, In particular, nylon 6 and nylon 66 are preferably used. A feature of the present invention is that a polyamide (B) having a relatively high melting point is used. More specifically, by molding the resin composition of the present invention at a temperature higher than the melting point of polyetheresteramide (A) and lower than the melting point of polyamide (B), polyamide (B) functions as a polymer nucleating agent. However, it becomes possible to impart the crystallinity, moldability, and melt viscosity that are the objectives of the present invention. These effects cannot be obtained when polyamides with relatively low melting points, such as nylon 11 and nylon 12, are used. In the present invention, polyether ester amide (A)
The mixing ratio of (A) and polyamide (B) is 50 to 99 parts by weight.
It is necessary to adjust the proportion of (B) to 50 to 1 part by weight. When (B) is less than 1 part by weight, the melting point of the present invention is increased;
The effect of improving high temperature properties is small, and if it exceeds 50 parts by weight, it impairs the flexibility and elastic recovery of the polyether ester amide, which is not preferred. The resin composition of the present invention is preferably melt-kneaded, and known methods can be used for melt-kneading. For example, the resin composition can be prepared by melt-kneading using a Banharry mixer, a rubber roll machine, a single-screw or twin-screw extruder, etc., usually at a temperature of 100 to 300°C. The resin composition of the present invention also includes known antioxidants, thermal decomposition inhibitors, ultraviolet absorbers, hydrolysis resistance improvers, colorants (pigments, dyes), antistatic agents, conductive agents, flame retardants, and reinforcing agents. Agents, fillers, lubricants, nucleating agents, mold release agents, plasticizers, adhesion aids, adhesives, etc. can be optionally contained. <Examples> Unless otherwise specified in the examples, parts mean parts by weight. Reference Example Polymerization of polymer (A-1) ω-aminododecanoic acid 81.9 parts, dodecanedioic acid
6.8 parts of poly(tetramethylene oxide) glycol and 19.3 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 650 were charged together with 0.5 parts of "Irganox" 1098 (antioxidant) into a reaction vessel equipped with a helical ribbon stirring blade, and the mixture was purged with nitrogen and heated at 260°C. After heating and stirring for 1 hour to obtain a homogeneous transparent solution, 0.015 parts of antimony trioxide catalyst,
Monobutyl monohydroxytin oxide catalyst 0.015
and 0.005 parts of phosphoric acid (anticoloring agent) were added, and the polymerization conditions were brought to below 1 mmHg in 1 hour according to a vacuum program. 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) has a relative viscosity (ηr) measured in orthochlorophenol at 25°C and a concentration of 0.5%.
was 1.81, and the crystal melting point by DSC was 167°C. Polymerization of polymer (A-2) 49.1 parts of ω-aminododecanoic acid, terephthalic acid
7.9 parts, 48.8 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 1020, 0.5 parts of "Irganox" 1098, 0.015 parts of antimony trioxide,
0.015 parts of monobutyl monohydroxytin oxide,
and 0.005 part of phosphoric acid under the same conditions as Polymer (A-1) to obtain polyetheresteramide (A-2) having a relative viscosity of 1.93 and a melting point of 154°C. Polymerization of polymer (A-3) 27.3 parts of ω-aminododecanoic acid, terephthalic acid
Polymer (A- Polymerization was carried out under the same conditions as in 1) to obtain polyether ester amide (A-3) having a relative viscosity of 1.92 and a melting point of 145°C. Polymerization of polymer (A-4) Undecamethylenediamine-adipate 44.9
12.8 parts of terephthalic acid, 50.0 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 650.
part, "Irganox" 1098 0.5 part, antimony trioxide 0.015 part, monobutyl monohydroxytin oxide 0.015 part, and phosphoric acid 0.005 part under the same conditions as Polymer (A-1), and the relative viscosity was 1.80.
Polyether ester amide (A-
4) was obtained. Polyamide The abbreviations and contents of polyamide (B) used in Examples and Comparative Examples are as follows.

[Table] Examples 1 to 7, Comparative Examples 3 and 4 (Comparative Examples 1, 2,
5 and 6 will be described later) Polyether ester amide block copolymers (A-1), (A-2), (A-3) and (A-4)
By mixing the polyamides shown in the table, (B-1), (B-2) and (B-3) were obtained depending on the polyamide used.
The mixtures were melt-kneaded in a 30 mmφ extruder heated to 250°C, 280°C, and 210°C, respectively, and then pelletized. The obtained pellets were molded into JIS No. 2 tensile test pieces using an injection molding machine with a 5 oz injection capacity at the molding temperature shown in the table and at a mold temperature of 40°C. Tensile properties meet ASTM D-638, and hardness meets ASTM D-638.
ASTM D-2240, melting index ASTM D-1238
Measured according to the following. The molding cycle was a holding time + cooling time to obtain a good molded product. The results are shown in the table. Comparative Examples 1, 2, 5, 6 Polyether ester amide (A-1), (A-
2) For (A-3) and (A-4), JIS No. 2 tensile test pieces were molded in the same manner as Examples 1 to 7 and Comparative Examples 3 and 4, and the tensile properties, hardness, melting index, and molding cycle were determined. Ta. The results are shown in the table.

【table】

[Table] <Effects of the invention> As seen in Examples 1 to 7, the resin composition of the present invention reduced the melting index and molding cycle while retaining the flexibility and excellent mechanical properties of polyetheresteramide. has high melt viscosity, crystallinity,
It can be seen that the moldability is excellent.

Claims (1)

[Claims] 1 Aminocarboxylic acid or lactam having 6 or more carbon atoms, or 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 6000, and number of carbon atoms Aminocarboxylic acid or lactam (d) having 4 to 9 carbon atoms and/or 4 to 9 carbon atoms to 50 to 99 parts by weight of polyether ester amide (A) composed of 4 to 20 dicarboxylic acids (c). A polyether ester amide resin composition prepared by mixing 50 to 1 part by weight of a polyamide (B) composed of a diamine and a dicarboxylic acid salt (e).