COMPOSITION OF A BLEND OF POLYAMIDE AND POLYESTER RESINS

Abstract

A resin blend composition of a polyamide resin and a polyester resin is described, which includes a polyamide resin, a polyester resin and an epoxy resin. The resin blend composition can have improved compatibility between the polyamide resin and the thermoplastic polyester resin, and therefore mechanical properties (strength, bending strength, elasticity, abrasion resistance, impact strength), chemical properties (solvent resistance), thermal resistance, dimensional stability, and paintability.

Claims

1-10. (canceled)

11. A resin blend composition of a polyamide resin and of a polyester resin, the composition comprising: a) from 1 wt. % to 98 wt. % of a thermoplastic polyamide resin; b) from 1 wt. % to 98 wt. % of a thermoplastic polyester resin comprising at least one C.sub.2-C.sub.20 aliphatic glycol as a diol monomer; c) from 0.01 wt. % to 10 wt. % of an epoxy resin having an epoxy equivalent weight (EEW) between 2100 g/eq and 6000 g/eq; and d) from 1 wt. % to 40 wt. % of a fireproofing agent comprising phosphorus selected from red phosphorus, melamine polyphosphate, aluminium diethyl phosphinate, and combinations thereof.

12. The composition as claimed in claim 11 comprising 5.5 wt. % to 20 wt. % of the fireproofing agent.

13. The composition as claimed in claim 11, wherein said epoxy resin comprises one or more elements selected from the group consisting of a diglycidyl ether of bisphenol A (DGEBA) epoxy resin, a diglycidyl ether of bisphenol F (DGEBF) epoxy resin, a hydrogenated bisphenol A (BPA) epoxy resin, a brominated epoxy resin, a cycloaliphatic epoxy resin, an epoxy resin of modified rubber, an aliphatic polyglycidyl epoxy resin, and a glycidyl amine epoxy resin.

14. The composition as claimed in claim 11, wherein the epoxy equivalent weight of said epoxy resin varies from 2500 g/eq to 6000 g/eq.

15. The composition as claimed in claim 11, wherein said composition comprises from 0.05 wt. % to 7 wt. % of said epoxy resin.

16. The composition as claimed in claim 11, wherein said polyamide resin comprises one or more elements selected from the group consisting of polyamide-6, polyamide-66, polyamide-610, polyamide-11, polyamide-12, polyterephthalamide, polyisophthalamide, and polyaramids.

17. The composition as claimed in claim 11, wherein said polyester resin comprises one or more elements selected from the group consisting of polybutylene terephthalate, polybutylene (terephthalate/isophthalate), polybutylene (terephthalate/adipate), polybutylene (terephthalate/sebacate), polybutylene (terephthalate/decanedicarboxylate), polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate/isophthalate), polyethylene (terephthalate/adipate), polyethylene (terephthalate/5-sodium sulfoisophthalate), polybutylene (terephthalate/5-sodium sulfoisophthalate), polypropylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethylene terephthalate.

18. The composition as claimed in claim 11, wherein said polyester resin is a recycled resin.

19. A method of preparing a resin blend composition of a polyamide resin and of a polyester resin, the method comprising mixing in the molten state: a) from 1 wt. % to 98 wt. % of a thermoplastic polyamide resin; b) from 1 wt. % to 98 wt. % of a thermoplastic polyester resin comprising at least one C.sub.2-C.sub.20 aliphatic glycol as a diol monomer; c) from 0.01 wt. % to 10 wt. % of an epoxy resin having an epoxy equivalent weight between 2100 g/eq and 6000 g/eq; and d) from 1 wt. % to 40 wt. % of a fireproofing agent comprising phosphorus selected from red phosphorus, melamine polyphosphate, aluminium diethyl phosphinate, and combinations thereof.

20. The method of claim 19 comprising 5.5 wt. % to 20 wt. % of the fireproofing agent.

21. A method of improving compatibility of a resin blend composition comprising a thermoplastic polyamide resin, a thermoplastic polyester resin, and a fireproofing agent comprising phosphorus selected from red phosphorus, melamine polyphosphate, aluminium diethyl phosphinate, and combinations thereof, the method comprising adding an epoxy resin having an epoxy equivalent weight between 2100 g/eq and 6000 g/eq to improve the compatibility of the resin blend composition.

22. The composition as claimed in claim 11, wherein the C.sub.2-C.sub.20 aliphatic glycol is selected from ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, and cyclohexanediol.

23. The method of claim 19, wherein the C.sub.2-C.sub.20 aliphatic glycol is selected from ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, and cyclohexanediol.

24. The composition as claimed in claim 11, wherein the thermoplastic polyester resin further comprises at least one dicarboxylic acid as a monomer.

25. The method of claim 19, wherein the thermoplastic polyester resin further comprises at least one dicarboxylic acid as a monomer.

26. The composition as claimed in claim 24, wherein the dicarboxylic acid is an aromatic dicarboxylic acid selected from terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4-diphenyl ether carboxylic acid, and 5-sodium sulfoisophthalic acid.

27. The method of claim 25, wherein the dicarboxylic acid is an aromatic dicarboxylic acid selected from terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4-diphenyl ether carboxylic acid, and 5-sodium sulfoisophthalic acid.

28. A resin blend composition of a polyamide resin and of a polyester resin, the composition comprising: a) from 1 wt. % to 98 wt. % of a thermoplastic polyamide resin selected from polyamide-6, polyamide-66, polyamide-66/6, and mixtures thereof; b) from 1 wt. % to 98 wt. % of a thermoplastic polyester resin selected from polybutylene terephthalate, polyethylene terephthalate, and mixtures thereof; c) from 0.1 wt. % to 5 wt. % of an epoxy resin selected from a diglycidyl ether of bisphenol A (DGEBA) having an epoxy equivalent weight (EEW) between 2100 g/eq and 6000 g/eq; and d) from 1 wt. % to 40 wt. % of a fireproofing agent comprising phosphorus selected from red phosphorus, melamine polyphosphate, aluminium diethyl phosphinate, and combinations thereof.

29. The composition as claimed in claim 28 comprising 5.5 wt. % to 20 wt. % of the fireproofing agent.

Description

EXPERIMENTAL SECTION

[0060] In the following examples and comparative examples, the resin blend composition of the present invention and the comparative composition are prepared, respectively, and their tensile strength, their elongation in tension, their processability, etc., are then compared, on the basis of which the superior effects of the resin blend composition of polyamide resin and polyester resin of the present invention are described in detail.

[0061] Initially, each component used in the examples and comparative examples of the present invention are classified and explained below, and they are indicated with reference symbols.

<Thermoplastic Polyamide Resin>

[0062] A-1: Polyamide-66 thermoplastic resin {trade name: Technyl 23A, manufactured by Rhodia}.
A-2: Polyamide-6 thermoplastic resin {trade name: Toplamide 1011, manufactured by Hyosung}.

<Thermoplastic Polyester Resin>

[0063] B-1: Polyethylene terephthalate resin {trade name: ESLON PET-2211, manufactured by Woongjin Chemical}.
B-2: Polybutylene terephthalate resin {trade name: TRIBIT 1500 NA, manufactured by Samyang Corporation}.
B-3: Polyethylene terephthalate resin recycled from bottles.

<Epoxy Resin>

[0064] C-1: Epoxy resin of the DGEBA type {epoxy equivalent weight: 3000 g/eq}, manufactured by Kykdo Chemical, Co., Ltd.
C-2: Epoxy resin of the DGEBA type {epoxy equivalent weight: 500 g/eq}, manufactured by Kykdo Chemical, Co., Ltd.
C-3: Ethylene resin grafted with a glycidyl methacrylate group. Trade name: Lotarder A8900, manufactured by Arkema.
C-4: Epoxy resin of the DGEBA type {epoxy equivalent weight: 2000 g/eq}

Examples 1 to 8 and Comparative Examples 1 to 9

[0065] In an illustrative embodiment, the components selected above are mixed uniformly in a super-mixer according to each mixture ratio of the examples and comparative examples. A twin-screw extruder (inside diameter 30 mm, L/D=30) is used. The temperatures of the barrel inside the extruder are set to about 250 C. when the polyamide-6 resin is used, and to about 280 C. when the polyamide-66 resin is used, taking into account the melting point of the resin used, and the gas within the screws is exhausted at a rotary speed of the screws from 250 to 300 rev/min and a vacuum pump pressure from 50 to 70 cm Hg. The components are perfectly mixed inside the extruder barrel and the strand formed is cooled rapidly in a bath of cold water and pelletized at a specified a size using a pelleter.

[0066] An injection molding machine (German, ENGEL) having a closing force of 80 tonnes and an injection volume of 189.44 cc (6.4 oz) is used for preparing samples for the various tests of properties. After preparing the sample of the composition by molding in conditions of a molding temperature in the general range taking account of the melting point of the resin used, a molding temperature of 80 C., an injection pressure from 50 to 80 bar, an injection speed from 40 to 60 mm/s, an injection time of three seconds and a cooling time of fifteen seconds.

[0067] The overall properties are measured by the following methods, and the results are presented in Tables 1-3 below.

[0068] The elements to be analyzed and the methods of analysis are as follows. [0069] Tensile strength: The tensile strength is measured using an Instron tester according to the method of analysis ASTM D-638. The unit of measurement of tensile strength is kgf/cm.sup.2. [0070] Elongation in tension: The tensile elastic modulus is measured using an Instron tester according to the method of analysis ASTM D-638. The unit of measurement of elongation in tension is %. [0071] Peeling: The sample prepared according to method ASTM D-638 is folded several times and it is examined to check for any peeling at the point of folding.

[0072] The standard is shown below:

##STR00001## [0073] Processability: The degree of swelling of the strand at extruder outlet is observed. The standard is shown below:

##STR00002##

TABLE-US-00001 TABLE 1 Component Exam- Exam- Exam- Exam- Exam- Exam- (wt. %) ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 A-1 57 57 40 59.7 A-2 57 40 B-1 40 57 40 B-2 40 40 57 C-1 3 3 3 3 3 0.3 Tensile 80 79 71 67 56 79 strength (MPa) Elongation in 120 70 90 130 100 30 tension (%) Peeling 5 5 5 5 5 5 Swelling 5 5 5 5 5 5

TABLE-US-00002 TABLE 2 Comp. Comp. Comp. Comp. Comp. Comp. Component Exam- Exam- Exam- Exam- Exam- Exam- (wt. %) ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 A-1 50 57 57 57 50 60 A-2 B-1 35 40 40 40 40 B-2 40 C-1 15 C-2 3 0.3 C-3 3 10 * Tensile 70 46 strength (MPa) * Elongation in 10 3 tension (%) * Peeling 4 3 * Swelling 1 1 3 2 3 1

TABLE-US-00003 TABLE 3 Comp. Comp. Comp. Component Exam- Exam- Exam- Exam- Exam- Exam- (wt. %) ple 7 ple 8 ple 8 ple 7 ple 8 ple 9 A-1 58.5 57.3 56.1 58.5 57.3 56.1 B-1 38 38.2 37.4 38 38.2 37.4 C-1 2 4 6 C-4 2 4 6 Elongation in 51.9 66.2 62.2 4.7 11.5 14.3 tension (%)

[0074] Based on the above Tables 1-3, it can be confirmed that compatibility was improved on adding an epoxy resin to a composition of a blend of polyamide resins 6 or of polyamide 66 and of polyethylene terephthalate or of polybutylene terephthalate without any compatibility. In the case of considerable swelling at extruder outlet through lack of compatibility (comparative example 4, comparative example 6), the properties and peeling could not be evaluated, as no pellet could be obtained.

[0075] In the case when a large amount of epoxy resin is added (comparative example 1), the viscosity of the resin blend composition is too high and processability is therefore found to be poor. The composition obtained by adding an epoxy resin having a low epoxy equivalent weight displays considerable swelling at extruder outlet and therefore the properties and peeling cannot be evaluated, as no pellet can be obtained (comparative example 2), or the processability and properties are lower compared with the composition of resins that uses epoxy resin presented in the present invention (comparative example 3).

[0076] In the case when compatibility is obtained by using an ethylene resin grafted with a glycidyl methacrylate group known in the prior art (comparative example 5), the rigidity, resistance and processability are all insufficient.

Examples 9 to 11

[0077] For producing compositions comprising recycled polyesters, the protocol is the same as mentioned above. The components selected above are employed according to each mixture ratio of the examples and are presented in the following table, with the properties indicated.

TABLE-US-00004 TABLE 4 Component (wt. %) Example 9 Example 10 Example 11 A-1 58.8 58.8 58.8 B-1 39.2 19.6 B-3 19.6 29.2 C-1 1.5 1.5 1.5 Tensile 788.1 783.4 797.9 strength Bending modulus 29 440 28 750 30 120 ASTM D790 (kgf/cm.sup.2) IZOD impact 4.34 4.01 4.20 ASTM D256 (kgf/cm/cm)

[0078] Mechanical properties that are equivalent and satisfactory are observed for the various formulations according to the invention.

Example 12 and Comparative Example 12

[0079] For the production of fireproofed compositions, the protocol is the same as mentioned above. The components are employed according to each mixture ratio of the examples and are presented in the following table, with the properties indicated.

TABLE-US-00005 TABLE 5 Component Example Comparative (wt. %) 12 example 12 A-1 34.08 51.2 B-1 22.72 C-1 0.6 Glass fibers 30 30 With organophosphorus 8.1 11.6 MPP 4.1 5.8 GWIT, 2 mm ( C.) 775 775 GWFI, 2 mm ( C.) 960 960 UL 94 0.8 mm VO V0 Tensile strength (MPa) 137.9 133.7

[0080] The organophosphorus compound is Exolit OP1230 from the company Clariant. MPP is melamine polyphosphate.

[0081] It can thus be seen that a blend according to the present invention makes it possible to obtain quite remarkable fireproofing properties, while using a smaller amount (30% reduction) of fireproofing agents in the formulation.

Example 13 and Comparative Example 13

[0082] For producing fireproofed compositions, the protocol is the same as mentioned above. The components are employed according to each mixture ratio of the examples and are presented in the following table, with the properties indicated.

TABLE-US-00006 TABLE 6 Component Example Comparative (wt. %) 12 example 12 A-1 47 51.2 B-1 20 C-1 1 Glass fibers 25 25 Red phosphorus 6.6 11 GWIT, 775 C., 1 mm Pass Pass GWIT, 775 C., 2 mm Pass Fail GWFI, 960 C., 1 mm Pass Pass GWFI, 960 C., 2 mm Pass Pass UL 94 0.8 mm V0 VO CTI (V) 450 425 Tensile strength (MPa) 167 167 Elongation at rupture (%) 3.1 3.1

[0083] The red phosphorus is RPM 460 FerroFlam.

[0084] It can thus be seen that a blend according to the present invention makes it possible to obtain quite remarkable fireproofing properties while using a smaller amount (40% reduction) of fireproofing agents in the formulation.

Advantageous Effect

[0085] A composition of a blend of resins with remarkably improved compatibility can be obtained by adding a specific epoxy resin to a blend of a polyamide resin and of a polyester resin, which are well known for having no compatibility. The blend of resins with improved compatibility can have excellent properties such as mechanical properties (strength properties, bending strength, elasticity, abrasion resistance, impact strength), chemical properties (resistance to solvents), heat resistance, dimensional stability, combability, etc.

[0086] Based on the foregoing, it will be understood that various embodiments of the present disclosure have been described here for purposes of illustration and that various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, the various embodiments described here are not intended to be limiting, the spirit and the real scope being indicated by the following claims.