JPH0314868B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a resin composition having excellent wear resistance, moldability, flexibility, and mechanical properties. [Prior Art] Polyetherester amides having polyamide repeating units, polyether repeating units and ester bonds in the polymer main chain are known (US Pat. No. 3,044,987). Thermoplastic polyurethane elastomers are also known. [Problems to be solved by the invention] Polyether ester amide has excellent lightness, transparency, and low-temperature impact resistance, and also does not cause burrs or burrs during molding.
Since it does not easily cause sink marks, it is promising for various molding applications, but there is still room for improvement in wear resistance. For example, abrasion resistance is particularly required in applications such as hoses, connectors, wire sheaths, and ski boots, and currently, their use in these applications is restricted. On the other hand, although thermoplastic polyurethane elastomers have excellent elastic recovery properties, abrasion resistance, and mechanical strength, they have problems in that they are inferior in thermal stability, hydrolysis resistance, moldability, and the like. The object of the present invention is to solve the above problems and provide a resin composition with excellent flexibility, moldability, abrasion resistance, and mechanical strength. [Means for Solving the Problems] The above object of the present invention is to provide at least one polyamide selected from aminocarboxylic acids having 6 or more carbon atoms, lactams, and salts of diamines and dicarboxylic acids having 6 or more carbon atoms. Forming component a, number average molecular weight
A resin consisting of a polyether ester amide (polymer A) derived from a poly(alkylene oxide) glycol b having 300 to 6000 carbon atoms and a dicarboxylic acid c having 4 to 20 carbon atoms, and a thermoplastic polyurethane elastomer (polymer B) This can be achieved by creating a resin composition in which polymer A is blended in an amount of 99 to 1% by weight and polymer B is blended in a proportion of 1 to 99% by weight based on the total composition. Hereinafter, the configuration, embodiments, and effects of the present invention will be explained in detail. 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 (polymer A) of the present invention include ω-aminocaproic acid, ω-aminoenanthic acid, , aminocarboxylic acids such as ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, or lactams such as caprolactam, enantholactam, capryllactam, laurolactam, and Diamine-dicarboxes such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate, hexamethylenediamine-isophthalate, undecamethylenediamine-adipate, 4,4'-diaminodicyclohexylmethane-dodecanedioate, etc. Although there are acid salts, 11-aminoundecanoic acid and 12-aminododecanoic acid are particularly preferred, and these may be used in combination depending on the purpose and use. It is also permissible to use a small amount of other amide-forming components as copolymerization components for purposes such as lowering the melting point of polyether ester amide or increasing adhesiveness. Poly(alkylene oxide) glycol b in the polyether ester amide (polymer A) of the present invention includes polyethylene glycol, poly(1,2- and 1,3-propylene oxide)
Examples include 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, heat resistance, Poly(tetramethylene oxide) glycol is preferably used because of the excellent physical properties of polyether ester amide, such as water resistance, mechanical strength, and elastic recovery. The number average molecular weight of poly(alkylene oxide) glycol can be used in the range of 300 to 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 is selected. varies depending on the type of poly(alkylene oxide) glycol. For example, 300 to 6000 for polyethylene glycol;
The molecular weight is particularly preferably 1000 to 4000, in the case of poly(propylene oxide) glycol 300 to 5000, particularly preferably 500 to 3000, and in the case of poly(tetramethylene oxide) glycol 500 to 3000, particularly preferably 500 to 2500. Areas are preferably used. The dicarboxylic acid c having 4 to 20 carbon atoms in the polyether ester amide (polymer A) of the present invention is terephthalic acid, isophthalic acid, naphthalene-
Aromatic dicarboxylic acids such as 2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, sodium 3-sulfoisophthalate, 1,4- cyclohexanedicarboxylic acid,
Alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid, and fatty acid dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, and dodecanedioic acid (decanedicarboxylic acid). can be mentioned. 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 notably, the copolymerization amount of poly(alkylene oxide) glycol b in the polyether ester amide (polymer A) is preferably 5 to 90% by weight. If the copolymerization amount is less than 5% by weight, flexibility and elastic recovery properties will be lost, and if it exceeds 90% by weight, high temperature properties and mechanical properties will be insufficient. The method for polymerizing polyether ester amide (polymer A) is not particularly limited, and any known method can be used. For example, there is a method in which an aminocarboxylic acid or lactam a and a dicarboxylic acid c are reacted to produce a polyamide prepolymer having carboxylic acid groups at both ends, and this is reacted with poly(alkylene oxide) glycol b under vacuum, or the method described in a. A method in which a carboxylic acid-terminated polyamide prepolymer is produced by charging the compounds b and c into a reaction tank and carrying out a heating reaction at high temperature in the presence or absence of water, and then proceeding with polymerization under normal pressure or reduced pressure. It has been known. There is also a method in which the above compounds a, b, and c are simultaneously charged into a reaction tank, melt-polymerized, and then polymerized all at once under high vacuum; this method is preferable since it causes less coloring of the polymer. The thermoplastic polyurethane elastomer (polymer B) of the present invention includes polyethylene glycol, poly(1,2- and 1,3-
- Poly(alkylene oxide) glycols such as propylene oxide) glycol, poly(tetramethylene oxide) glycol, or aliphatic polyester glycols such as polyethylene adipate, polytetramethylene sebacate, polycaprolactone, tolylene diisocyanate, diphenyl A copolymer obtained by reacting an aromatic diisocyanate such as methane diisocyanate and extending the chain of a prepolymer having an isocyanate group at the end with water, a glycol such as ethylene glycol, or a diamine such as hydrazine, ethylene diamine, and propylene diamine. Coalescing may be used. As an example, molecular weight 1000~
3000 poly(tetramethylene oxide) glycol or polyethylene adipate is reacted with an excess mole of diphenylmethane diisocyanate, and the chain is extended with hydrazine. In the present invention, the blending ratio of polyether ester amide (polymer A) and thermoplastic polyurethane elastomer (polymer B) is such that A is 99 to 1% by weight, preferably 95 to 5% by weight based on the total composition. %,
More preferably 80 to 20% by weight, B 1 to 99% by weight, preferably 5 to 95% by weight, even more preferably
It is necessary to adjust the content to 20 to 80% by weight. If B is less than 1% by weight, the wear resistance of the present invention will not be sufficient, and if it exceeds 99% by weight, moldability will be impaired, which is not preferable. The present invention is characterized by extremely good compatibility between the polyether ester amide and the thermoplastic polyurethane elastomer, and the effects of the present invention cannot be obtained with ordinary incompatible polymer blends. Furthermore, surprisingly, the breaking strength of the resin composition of the present invention exceeds the arithmetic mean of the breaking strength values of each component polymer, which also indicates good compatibility. 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 Banbury 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] Examples 1 to 9 In the examples, unless otherwise specified, parts mean parts by weight. (1) Production of polymer A ● 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 parts of phosphoric acid and 0.005 parts of phosphoric acid (anticoloring agent) were added, and the polymerization conditions were brought to 1 mmHg or less 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) had a relative viscosity (ηr) of 1.81 when measured in orthochlorophenol at 25°C at a concentration of 0.5%, and a crystal melting point by DSC of
It was 167℃. ● 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 parts of phosphoric acid under the same conditions as polymer (A-1), relative viscosity 1.93, melting point 154℃
A polyether ester amide (A-2) was obtained. ● Polymerization of polymer (A-3) ω-aminododecanoic acid 27.3 parts, terephthalic acid
5.7 parts, 70.5 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 2060, 0.5 parts of "Irganox" 1098, 0.015 parts of antimony trioxide,
0.015 parts of monobutyl monohydroxytin oxide,
Polymerized from 0.005 parts of phosphoric acid under the same conditions as Polymer (A-1), with a relative viscosity of 1.92 and a melting point of 145°C.
A polyether ester amide (A-3) was obtained. (2) Production of Polymer B ● Production of Polymer (B-1) 41.6 parts of diphenylmethane diisocyanate and 50.9 parts of poly(ethylene adipate) glycol with a number average molecular weight of 1400 are mixed and heated to form a polymer having an isocyanate group at the end. A polymer was obtained. Ethylenediamine is added to this prepolymer as a chain extender.
By adding 7.5 parts and heating reaction, MI=
A polymer (B-1) of 5.3 (200° C., 2160 g load) was obtained. ● Production of polymer (B-2) 36.4 parts of diphenylmethane diisocyanate, 53.0 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 1900, and butanediol.
Polymerize from 10.6 parts in the same manner as polymer (B-1),
Polymer (B-
2) was obtained. ● Production of polymer (B-3) 46.8 parts of diphenylmethane diisocyanate, poly(ε-caprolactone) with a number average molecular weight of 1000.
Polymerize from 40.0 parts and 13.2 parts of butanediol in the same manner as polymer (B-1), MI=1.9 (200℃,
A polymer (B-3) with a weight of 2160 g was obtained. (3) Production of composition and measurement of physical properties The polyurethane shown in the table was mixed with the polyether ester amide block copolymers (A-1), (A-2) and (A-3), and the mixture was heated to 200°C. Ta
The mixture was melt-kneaded using a 30 mmφ extruder and then pelletized. The obtained pellets were molded into JIS No. 2 tensile test pieces using an injection molding machine having a 5 oz injection capacity at a molding temperature of 200°C and a mold temperature of 40°C. Tensile properties were measured according to ASTM D-638, and Taber wear was measured according to ASTM D-1044 (CS-17Wheel). 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 to 6 Polyether ester amide (A-1), (A-
2) and (A-3), polyurethane (B-1),
Examples 1 to (B-2) and (B-3)
JIS No. 2 tensile test pieces were molded in the same manner as in 9, and the tensile properties, Taber abrasion resistance, and molding cycles were determined. The results are shown in the table.

【table】

[Table] *Blending ratios indicate parts by weight.
<Effects of the Invention> As seen in Examples 1 to 9, the resin composition of the present invention has excellent flexibility, moldability, abrasion resistance, and mechanical strength.

Claims (1)

[Claims] 1 At least one polyamide-forming component a selected from aminocarboxylic acids having 6 or more carbon atoms, lactams, and salts of diamines and dicarboxylic acids having 6 or more carbon atoms, poly(alkylene oxide) glycol having a number average molecular weight of 300 to 6000 b, and a polyether ester amide (polymer A) derived from a dicarboxylic acid having 4 to 20 carbon atoms (c) and a thermoplastic polyurethane elastomer (polymer B), the resin composition comprising: A resin composition characterized in that Polymer A is blended in a proportion of 99 to 1% by weight, and Polymer B is blended in a proportion of 1 to 99% by weight.