KR20100121131A - Thermoplastic polyester resin composition with low gloss property and heat resistance - Google Patents

Abstract

PURPOSE: A thermoplastic polyester resin composition is provided to secure the excellent weather ability, heat resistance, quenched property, and low temperature impact-resistance property. CONSTITUTION: A thermoplastic polyester resin composition contains 10~60wt% of thermoplastic polyester resin, 10~70wt% of aromatic polycarbonate resin, 5~30wt% of impact reinforcing agent resin, 0.5~6wt% of quenching agent, and 0.01~10wt% of weather resistant stabilizer. The thermoplastic polyester resin is selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, modified polybutylene terephthalate, and other compounds.

Description

Thermoplastic Polyester Resin Composition With Low Gloss Property And Heat Resistance}

The present invention relates to a thermoplastic polyester resin composition having improved matting properties and heat resistance, and more particularly to a thermoplastic polyester resin composition having excellent low temperature impact resistance, matting properties, heat resistance and weather resistance.

Thermoplastic polyester resins are excellent in mechanical and electrical properties and other physical and chemical properties, and are being applied to a wide range of fields including automobile parts, electrical and electronic devices, and office equipment.

Among the polyester resins, polybutylene terephthalate (poly (butylene terephthalte), PBT) is typically included in the five general-purpose engineering plastics due to its excellent electrical properties and excellent moldability of crystalline plastics. It lacks the low temperature impact resistance and heat resistance required for automobile parts.

On the other hand, the aromatic polycarbonate resin has advantages such as excellent heat resistance, impact resistance and dimension stability, but has a disadvantage of low molding processability and chemical resistance.

Accordingly, US Pat. No. 4,906,202 and US Pat. No. 4,393,153, etc., alloy the polybutylene terephthalate and the aromatic polycarbonate resin to improve low impact resistance, heat resistance and workability, which are pointed out as disadvantages when used alone. Was intended.

In addition, US Pat. No. 5,114,998 discloses a resin composition in which a thermoplastic polyester resin blend includes talc, butadiene-based impact modifiers and stabilizers to prevent decomposition of the resin blend. A resin composition comprising butadiene-based core-shell polymer as an impact modifier has been disclosed.

In addition, U.S. Patent No. 4,460,731 discloses a resin composition for reinforcing glass fibers in a blend of polybutylene terephthalate and polyethylene terephthalate (PET) to suppress warpage of molded articles. Strength and hardness are improved by adding glass fiber, halogen flame retardant, antimony trioxide, etc. to the blend of butylene terephthalate and polyethylene terephthalate (PET), and transesterification reaction in resin (PET and PBT in resin during processing) The resin composition in which the reaction which cross-linking takes place between) is suppressed is disclosed.

However, the patented technologies are difficult to express sufficient impact resistance and heat resistance due to the low dispersion of shock beams, etc. introduced into the polymer alloy (or blend), and also lack the matting properties and weather resistance required for automobile exterior materials. There is.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a thermoplastic polyester resin composition excellent in low-temperature impact resistance, matting properties, heat resistance and weather resistance.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention is A) 10 to 60% by weight thermoplastic polyester resin; B) 10 to 70% by weight aromatic polycarbonate resin; C) 5 to 30% by weight of impact modifier resin; D) 0.5 to 6 wt% matting agent; And E) 0.01 to 10% by weight of weathering stabilizer; provides a thermoplastic polyester resin composition with improved matting and heat resistance.

As described above, according to the present invention, a predetermined impact modifier, a matting agent, a weather stabilizer, and the like are mixed with a polymer alloy made of a thermoplastic polyester and an aromatic polycarbonate resin, thereby providing excellent low temperature impact resistance, quenching property, heat resistance and weather resistance. There is an effect of providing a thermoplastic polyester resin composition.

Hereinafter, the present invention will be described in detail.

The thermoplastic polyester resin composition having improved matting and heat resistance of the present invention comprises: A) 10 to 60% by weight of a thermoplastic polyester resin; B) 10 to 70% by weight aromatic polycarbonate resin; C) 5 to 30% by weight of impact modifier resin; D) 0.5 to 6 wt% matting agent; And E) 0.01 to 10% by weight of a weathering stabilizer.

The thermoplastic polyester resin A) may be a polymer prepared by direct esterification or transesterification (condensation polymerization) of terephthalate or dimethyl terephthalate and a diol compound.

In addition, the A) thermoplastic polyester resin may be a modified thermoplastic polyester resin modified to increase the impact strength.

The modified thermoplastic polyester resin is selected from the group consisting of polytetramethylene glycol (PTMG), polypropylene glycol (PPG), polyethylene glycol (PEG), low molecular weight aliphatic polyester and low molecular weight aliphatic polyamide during the condensation polymerization. It may be a polymerized copolymer further comprising one or more.

The A) thermoplastic polyester resin, more specifically, at least one selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, polytrimethylene terephthalate, and the like. Can be.

The A) thermoplastic polyester resin may be included in 10 to 60% by weight based on the total amount of the resin composition (A ~ E), preferably contained in 20 to 50% by weight, if less than 10% by weight heat resistance, tensile It is difficult to expect an improvement in strength and the like, and when it exceeds 60% by weight, there is a problem that the impact resistance is not sufficient.

The B) aromatic polycarbonate resin may be a polymer in which bisphenol-A and phosgene are polycondensed or a polymer in which bisphenol-A and diphenyl carbonate are polycondensed by a transesterification reaction.

In addition, the B) aromatic polycarbonate resin may be at least one member selected from the group consisting of homopolycarbonate, copolycarbonate and terpolycarbonate.

As a specific example, the copolycarbonate may be a copolymer obtained by polymerization of bisphenol-A with phosgene or diphenyl carbonate by adding a comonomer such as resorcinol and hydroquinone.

The B) the aromatic polycarbonate resin may have a number average molecular weight of 5,000 to 200,000, but less than 5,000 impact resistance is lowered, if more than 200,000 there is a problem that the molding of the product is not easy because the flow characteristics are low.

The B) aromatic polycarbonate resin may be included in 10 to 70% by weight based on the total amount of the resin composition (A ~ E), preferably contained in 20 to 60% by weight, less than 10% by weight of the resin composition It cannot be expected to improve the heat resistance, and if it exceeds 70% by weight, there is a problem in that the molding property is lowered due to poor flow characteristics.

The C) impact modifier resin is not particularly limited in the case of a resin that can improve impact resistance, specifically, a methacrylonitrile-butadiene-styrene copolymer (MBS) having a core (rubber) -shell (plastic) structure, Acrylic rubbers such as acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-EPDM-styrene copolymer (AES) and acrylonitrile-butylacrylate-styrene (ASA) copolymer; Ethylene-propylene-diene terpolymers (EPDM); Styrene-butadiene-styrene copolymers (SBS); Styrene-isoprene-styrene copolymer (SIS); Styrene-butadiene copolymer (SB); Styrene-isoprene rubber; Ethylene-vinylacetate copolymer (EVA); Ethylene-ethylacrylate copolymer (EEA); Ethylene-vinyl alcohol copolymer (EVOH); PBT-based elastic body; PET-based elastic body; And nylon-based elastomers; It may be one or more selected from the group consisting of.

The C) impact modifier resin may be included in 5 to 30% by weight, preferably 5 to 20% by weight, more preferably 6 to 15% by weight based on the total amount of the resin composition (A ~ E). It is included as, if less than 5% by weight is difficult to expect the improvement of impact resistance at low temperatures, when it exceeds 30% by weight there is a problem that the heat resistance and mechanical strength is lowered.

For reference, the polyester resin composition consisting of only the polyester resin, the aromatic polycarbonate resin and the impact modifier resin may be limitedly applied to interior articles that do not specifically require heat resistance and appearance characteristics.

However, a separate component is required for wide application to exterior materials or parts of automobiles that require excellent heat resistance, impact resistance, and appearance characteristics. The present invention provides a predetermined quenching method for improving surface matting characteristics and weather resistance. Confectionery and weathering stabilizers were introduced.

The D) matting agent is to suppress the surface gloss by forming light irregularities on the surface of the product during injection molding to induce light scattering, it may be an ethylene glycidyl methacrylate-based compound, crosslinked styrene or a mixture thereof The ethylene glycidyl methacrylate compound may be ethylene glycidyl methacrylate grafted with maleic anhydride or ethylene glycidyl methacrylate grafted with vinyl acetate.

For reference, the ethylene glycidyl methacrylate-based impact modifier may be present in various forms depending on the glycidyl methacrylate content and the type of terminal reactor.

The D) matting agent may be included in an amount of 0.5 to 6% by weight with respect to the total amount of the resin composition (A ~ E), more preferably 1 to 5% by weight, when less than 0.5% by weight the low matting effect When it exceeds 6% by weight, there is a problem that the physical properties and workability is degraded.

The E) weather stabilizer imparts weather resistance to the resin composition, and is a benzotriazole type such as 2- (2'-hydroxy-3'-tertiary-butyl-5-methylphenyl) -5-chloro-benzotriazole and the like. Stabilizer, sebacate halide stabilizer such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, etc., 2- (4,6-diphenyl-1,3,5-triazine Triazine stabilizers such as 2-yl) -5-hexoxy-phenol and the like, benzophenone stabilizers such as 2-hydroxy-4-n-octyloxybenzophenol and the like, poly-{[6- (1,1,3 , 3-tetramethylbutyl-imino) -1,3,5-triazino-2,2-diyl] [2- (2,2,6,6-tetramethylpiperidinyl) -amino] -hexamethylene -[4- (2,2,6,6-tetra-methylpiperidinyl) imino]} and poly {(6-morpholino-s-strazine-2,4-diyl) [(2,2, 6,6-tetramethyl-4-piperidinyl) imino] -hexane [(2,2,6,6-tetramethyl-4-piperidinyl) imino]} or the like selected from the group consisting of It is desirable Do.

The E) weather stabilizer is preferably included in an amount of 0.01 to 10% by weight based on the total amount of the resin composition (A ~ E), if less than 0.01% by weight of the anti-oxidation effect of the resin composition lacks the effect of improving weather resistance, When it exceeds 10% by weight, there is a problem in that the economic efficiency is lowered due to the cost increase and the physical properties are lowered.

The thermoplastic polyester resin composition may be a lubricant, an antioxidant, a heat stabilizer, a light stabilizer, a hydrolysis inhibitor, a release agent, a pigment (specifically, such as carbon black, etc.), an antistatic agent, and a conductivity within a range not deteriorating physical properties as other additives. First, may further include one or more selected from the group consisting of EMI (electromagnetic interference) shielding agent, magnetic imparting agent, crosslinking agent, antimicrobial agent, processing aid, metal deactivator, anti-friction agent, anti-wear agent and coupling agent.

As a specific example of the method for producing the thermoplastic polyester composition, a compound corresponding to A) to E) and other additives are added to a supermixer and mixed, and then the mixture is mixed with a single screw extruder, a twin screw extruder, and a roll mill. After extruding by melt kneading using a compounding machine such as a kneader or a banbury mixer, the extrudate is pelleted using a pelletizer, and then sufficiently extruded in a dehumidifying or hot air dryer. After drying, it may be injection molded to finally prepare an injection molded article of the thermoplastic polyester resin composition.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

[Example]

Examples 1-5

The ingredients shown in Table 1 were added to the supermixer in the amounts shown, mixed, and then melt-kneaded and extruded using a twin screw extruder, and then the extrudate was manufactured into pellets using thermoplastic pellets. It was.

The prepared pellets were sufficiently dried in a hot air dryer, and then injection molded to prepare injection molded specimens of the thermoplastic polyester resin composition.

Comparative Examples 1 to 3

It was carried out in the same manner as in Example 1 except for using the components and contents shown in Table 1 below.

For reference, Comparative Example 1 did not include a quencher and a weathering stabilizer, Comparative Example 2 did not include a quencher, and Comparative Example 3 did not include a weathering stabilizer.

[Test Example]

The physical properties of the injection molded specimens of the thermoplastic polyester resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 1 below.

* Tensile strength and elongation: It was measured according to ASTM D638.

* Flexural Strength and Flexural Modulus: measured according to ASTM D790.

Impact strength: measured according to ASTM D256 (1/4 inch thick, Notched Izod).

* Heat resistance: measured according to ASTM D648.

* Weather resistance: delta-E measurement after Weather-O-meter 2500kJ

Surface gloss: gloss was measured by a glossmeter (60 degrees).

division Example Comparative example One 2 3 4 5 One 2 3 Furtherance/
weight% PBT resin 30 30 30 30 30 30 30 30 Polycarbonate 63 62 58 55 58 65 63 64 Impact modifier 5 5 5 11 5 5 5 5 Matting agent One 2 5 2 2 - - One Weather stabilizer One One 2 2 5 - 2 - Carbon black 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Properties Tensile strength (kgf / cm ² ) 550 540 520 460 540 560 560 560 % Elongation > 100 > 100 60 > 100 > 100 > 100 > 100 > 100 Flexural Strength (kgf / cm ² ) 760 750 740 680 740 750 760 760 Flexural modulus
(kgf / cm ² ) 20900 20400 20400 18900 20600 21000 20900 20300 Impact strength
(kgfcm / cm) 36 34 15 57 29 39 36 34 Weather stability
(delta-E) 1.4 1.2 1.2 1.9 0.9 1.6 1.2 1.5 Heat deflection temperature (℃) 105 106 104 98 106 105 105 106 Surface glossiness 34 21 12 24 21 97 99 37

As shown in Table 1, the thermoplastic polyester resin compositions (Examples 1 to 5) of the present invention have impact strength and heat resistance as compared with the case without the matting agent and / or weather stabilizer (Comparative Examples 1 to 3). And weathering stability are similar, but it was confirmed that the matting characteristic is remarkably excellent (surface gloss is significantly low).

Claims (10)

A) 10 to 60 wt% of the thermoplastic polyester resin; B) 10 to 70% by weight aromatic polycarbonate resin; C) 5 to 30% by weight of impact modifier resin; D) 0.5 to 6 wt% matting agent; And E) 0.01 to 10% by weight of weathering stabilizer; characterized in that comprises Thermoplastic polyester resin composition with improved low temperature impact and heat resistance. The method of claim 1, The A) thermoplastic polyester resin is polybutylene terephthalate, polyethylene terephthalate, modified polybutylene terephthalate, modified polyethylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate and polytrimethylene tere At least one member selected from the group consisting of phthalates Thermoplastic polyester resin composition with improved low temperature impact and heat resistance. The method of claim 1, Said C) impact modifier resin is a methacrylonitrile- butadiene-styrene copolymer, an acrylonitrile- butadiene-styrene copolymer, an acrylonitrile-EPDM-styrene copolymer, an acrylonitrile- butylacrylate-styrene copolymer , Ethylene-propylene-diene terpolymer (EPDM), styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene copolymer, styrene-isoprene rubber, ethylene-vinylacetate copolymer, ethylene-ethyl At least one member selected from the group consisting of an acrylate copolymer and an ethylene-vinyl alcohol copolymer Thermoplastic polyester resin composition with improved low temperature impact and heat resistance. The method of claim 1, The D) matting agent is an ethylene glycidyl methacrylate compound, crosslinked styrene or a mixture thereof Thermoplastic polyester resin composition with improved low temperature impact and heat resistance. The method of claim 4, wherein The ethylene glycidyl methacrylate compound is ethylene glycidyl methacrylate grafted with maleic anhydride, ethylene glycidyl methacrylate grafted with vinyl acetate, or a mixture thereof. doing Thermoplastic polyester resin composition with improved low temperature impact and heat resistance. The method of claim 1, The said E) weather stabilizer is a benzotriazole stabilizer, a sebacate halide stabilizer, a triazine stabilizer, a benzophenone stabilizer, poly {[6- (1,1,3,3- tetramethylbutyl- imino) -1. , 3,5-triazino-2,2-diyl] [2- (2,2,6,6-tetramethylpiperidinyl) -amino] -hexamethylene- [4- (2,2,6,6 -Tetra-methylpiperidinyl) imino]}, and poly {(6-morpholino-s-strazine-2,4-diyl) [(2,2,6,6-tetramethyl-4-piperidi Nil) imino] -hexane [(2,2,6,6-tetramethyl-4-piperidinyl) imino]}, or a compound selected from the group consisting of Thermoplastic polyester resin composition with improved low temperature impact and heat resistance. The method of claim 6, The said benzotriazole stabilizer is 2- (2'-hydroxy-3'-tert-butyl-5-methylphenyl) -5-chloro- benzotriazole, and the sebacate halide stabilizer is bis- (2,2 , 6,6-tetramethyl-4-piperidinyl) sebacate, and the triazine stabilizer is 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexoxy -Phenol, and the benzophenone-based stabilizer is 2-hydroxy-4-n-octyloxybenzophenol Thermoplastic polyester resin composition with improved low temperature impact and heat resistance. The method of claim 1, The thermoplastic polyester resin composition may include a lubricant, an antioxidant, a heat stabilizer, a light stabilizer, a hydrolysis inhibitor, a release agent, a pigment, an antistatic agent, a conductivity providing agent, an EMI shielding agent, a magnetic imparting agent, a crosslinking agent, an antibacterial agent, a processing aid, a metal It further comprises at least one member selected from the group consisting of an inactivating agent, an antifriction agent, an anti-wear agent and a coupling agent. Thermoplastic polyester resin composition with improved low temperature impact and heat resistance. An article made of the thermoplastic polyester resin composition of claim 1. The method of claim 9, The product, characterized in that the electrical, automotive or industrial parts.