KR100431534B1 - Polybutyleneterephthalate Resin Composition - Google Patents

Abstract

The filler-reinforced PBT resin composition of the present invention comprises (A) PBT resin, (B) PET resin, (C) polycarbonate (PC) resin, (D) impact modifier resin, optionally (E) styrene-acrylonitrile (I) 4 to 60 parts by weight of (I) inorganic filler based on 100 parts by weight of a resin mixture consisting of (styrene-acrylonitril: SAN) resin, (F) ultra high molecular weight SAN resin, (G) main flame retardant, and (H) flame retardant aid. The resin mixture includes (A) 25 to 93% by weight of PBT resin, (B) 1 to 40% by weight of PET resin, (C) 1 to 40% by weight of PC resin, (D) 1 to 40% by weight of impact modifier resin, ( E) 0-40 weight% of SAN resin, (F) 0.1-10 weight% of ultra high molecular weight SAN resin, (G) 1.0-30 weight% of main flame retardants, and (H) 0-10 weight% of flame retardant aids.

Description

Improved polybutylene terephthalate resin composition {Polybutyleneterephthalate Resin Composition}

Field of invention

The present invention relates to a polybutylene terephthalate (PBT) resin composition. More specifically, the present invention relates to a PBT resin composition reinforced with an inorganic filler and added with a crystalline polymer and an amorphous polymer to improve appearance and improve flowability and impact strength.

Background of the Invention

In general, PBT resin has a high crystallization rate, high flowability, and is widely used in electrical, electronic, automotive mechanical parts, etc. because of excellent weather resistance, electrical insulation, chemical resistance, and abrasion resistance. PBT resin, like other crystalline resins, improves the mechanical properties such as tensile strength and flexural strength and basic properties such as heat resistance when reinforcing glass fibers or other inorganic fillers. However, when a large amount of glass fiber or other inorganic filler is used, the surface of the final molding is very poor due to the surface protrusion of the inorganic fillers during the processing of injection molding, which is difficult to apply to a molded article requiring a beautiful exterior surface. It is true.

The present invention relates to a filler-reinforced positive appearance high gloss PBT resin composition that can be applied to a product having excellent surface appearance such as electric, electronic products, and automotive parts by making the surface appearance beautiful during molding.

In general, in order to improve the appearance of the molded article of the filler-reinforced PBT resin, a technique of adding polyethylene terephthalate (PET) having a slower crystallization rate compared to PBT has been used. However, the PBT resin composition is delayed in crystallization at the time of molding due to the addition of PET, thereby degrading molding workability. In addition, the PBT resin composition cannot sufficiently achieve both positive appearance and high gloss when using 15% by weight or more of glass fibers or using an impact modifier such as rubber for reinforcing impact resistance.

In order to solve the above drawbacks of the conventional PBT resin composition, the present inventors have come to develop a new PBT resin composition having a beautiful appearance and excellent gloss of a molded article.

An object of the present invention is to provide a filler-reinforced polybutylene terephthalate resin composition in which the molded article has a good appearance and excellent gloss.

Another object of the present invention is to provide a filler-reinforced PBT resin composition having a good appearance and gloss as well as good physical properties such as impact strength and tensile strength.

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

The filler-reinforced PBT resin composition of the present invention comprises (A) PBT resin, (B) PET resin, (C) polycarbonate (PC) resin, (D) impact modifier resin, optionally (E) styrene-acrylonitrile (I) 4 to 60 parts by weight of (I) inorganic filler based on 100 parts by weight of a resin mixture consisting of (styrene-acrylonitril: SAN) resin, (F) ultra high molecular weight SAN resin, (G) main flame retardant, and (H) flame retardant aid. The resin mixture includes (A) 25 to 93% by weight of PBT resin, (B) 1 to 40% by weight of PET resin, (C) 1 to 40% by weight of PC resin, (D) 1 to 40% by weight of impact modifier resin, ( E) 0-40 weight% of SAN resin, (F) 0.1-10 weight% of ultra high molecular weight SAN resin, (G) 1.0-30 weight% of main flame retardants, and (H) 0-10 weight% of flame retardant aids.

Each component for manufacturing the filler reinforced PBT resin composition of this invention is as follows.

(A) PBT resin

PBT resins are prepared by the polymerization of dicarbonic acid and diol compounds. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl sulfone dicarboxylic acid, and the like. As the diol component, α, ω -diol is used, examples of which are trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexanedimethylol, 2,2-bis (4- β hydroxy) Phenyl-phenyl) propane, 4,4-bis ( β -hydroxyepoxy) diphenyl sulfone, diethylene glycol and the like. PBT resins are used in amounts of 25 to 93% by weight in the resin mixture.

(B) PET resin

PET resin is prepared by the polymerization of dicarbonic acid and diol compound. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl sulfone dicarboxylic acid, and the like. The diol component is α, ω -diol, a representative example is ethylene glycol. PET resin is used in an amount of 1 to 40% by weight in the resin mixture.

(C) PC resin

Component (C) PC may be used homopolycarbonebolite, copolycarbonate, terpolycarbonate, or mixtures thereof. As for the molecular weight of PC, 10000-50000 (weight average molecular weight) are used normally. PC can be synthesized by interfacial polycondensation of phosgene and dihydroxy compounds, and the detailed method is described in German Patent Nos. 2063050, 2030305, 1570703, 2211956, and French Patents 1515851 and H. Schnell. "Chemistry and Physics of Polycarbonates" (Interscience Press, 1964).

(D) impact modifier resin

Component (D) is an olefinic rubber copolymer, a styrenic rubber copolymer, a polyester elastomeric impact modifier, and the like, and when a certain amount is added, the long-term heat resistance and hydrolysis resistance are excellent. Olefin rubber copolymers Impact modifiers include ethylene propylene copolymers (EPM) and ethylene propylene dienecopolymers (EPDM). Styrene rubber copolymers include block styrene-butadiene copolymers. In addition, styrene- ethylene- butylene- styrene-based (SEBS) impact modifier is also effective. As the polyester elastomer, a hard segment is polybutylene terephthalate, and a soft segment is polytetramethylene oxide glycol, and the polytetramethylene oxide glycol component is used as the weight-weight ratio of the entire elastomer. Products with 10-70% are used.

(E) SAN resin

Component (E) SAN resin is a resin produced by copolymerizing a styrene-based monomer and a vinyl cyan-based monomer by a method such as emulsion polymerization, suspension polymerization, or bulk polymerization, and can arbitrarily control each component depending on the intended use. Styrene monomers include styrene, α -methylstyrene, p-methylstyrene, and the like. Component (E) is a copolymer which usually contains 2 to 45 weight% of acrylonitrile, and is resin which has a weight average molecular weight of 50,000-500,000.

(F) Ultra High Molecular Weight SAN Resin

Component (F) The ultra-high molecular weight SAN resin is a resin produced by copolymerizing a styrene monomer and a vinyl cyan monomer by a method such as emulsion polymerization, suspension polymerization, or bulk polymerization, and can arbitrarily control each component according to the purpose of use. Styrene monomers include styrene, α -methylstyrene, p-methylstyrene, and the like. Component (F) is a copolymer usually containing 2 to 45 wt% of acrylonitrile, and is a resin having a weight average molecular weight of 2,000,000 to 20,000,000. Ultra high molecular weight SAN resins are used in amounts of 0.1 to 10% by weight in the resin mixture.

(G) main flame retardant

As the component (G) main flame retardant, a brominated epoxy or brominated polycarbonate-based compound is used. The main flame retardant is preferably 1.0 to 30% by weight, more preferably 5 to 20% in the resin mixture.

(H) Flame retardant

As the component (H) flame retardant aid, antimony trioxide is preferred. Antimony trioxide is used in an amount of 0 to 10% by weight in the resin mixture.

(I) weapon filler

Component (I) inorganic fillers are typically glass fibers, and conventional chopped strands may be used as the glass fibers, and a coulpling agent may be used to increase adhesion with the resin. Other inorganic fillers include carbon fiber, ceramic fiber, boron fiber, potassium titanate fiber, asbestos, calcium carbonate, silicate, alumina, aluminum hydroxide, talc, clay, mica, glass powder, glass beads, barium sulfate, whiskers, etc. do. The inorganic filler is composed of 4 to 60 parts by weight based on 100 parts by weight of the resin mixture.

The filler-reinforced PBT resin composition according to the present invention is in addition to the above-mentioned compositions (A), (B), (C), (D), (E), (F), (G), (H), and (I). Stabilizers, antioxidants, mold release agents, anti-dripping agents, pigments, inorganic additives and the like can also be added. In this case, each content is 0.1 to 5.0% by weight based on (A), (B), (C), (D), (E), (F), (G), (H), and (I). Is preferred.

The invention can be better understood by the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

As shown in the composition of Table 1, PBT resin compositions of Examples 1-3 and Comparative Examples 1-6 were prepared. In the mixing of the PBT resin composition of Example 1-3 and Comparative Example 1-6, the composition was uniformly mixed for 5 minutes in a Henschel mixer, and then introduced into a twin screw extruder having L / D = 29 and Φ = 40 mm. Glass fibers were introduced in the middle of the extruder using a side feeder. Extruded at a temperature of 24 ℃, 250rpm to produce a pellet (pellet).

The prepared pellets were prepared in a 10 Oz injection machine at an injection temperature of 250 ° C. and a mold temperature of 80 ° C., and then left at 23 ° C. and a relative humidity of 50% for 40 hours, and then measured for physical properties according to the ASTM method.

Pellets made to evaluate the appearance and glossiness of the specimens. The injection jet was produced by changing the injection speed of 100 mm diameter and 3 mm thick original specimens with a injection temperature of 250 ° C and a mold temperature of 80 ° C in a 10 OZ injection machine. In addition, after the specimen was prepared and left for 40 hours at 23 ° C. and a relative humidity of 50%, the specimen was measured for glossiness using a gloss measurement equipment.

According to the above formulation and test method, it was carried out according to the resin compositions of Examples and Comparative Examples of the present invention as follows to obtain the experimental results as shown in Table 1.

Property measurement

(1) Tensile strength (kgf / cm ² ): It was measured by the ASTM D638 method.

(2) Impact strength (1/8 ") (kgcm / cm): It measured by the ASTM D256 method.

(3) Glossiness (%): Measured by VGS-SENSOR of Nippon Densoku Kogyo Company Ltd.

(* ^(Note) : Not occurred at 100% injection rate, all components in Table 1 are parts by weight)

The present invention has the effect of the invention that the molded article can provide a filler-reinforced PBT resin composition having not only good appearance and gloss but also good physical properties such as impact strength and tensile strength.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (6)

(A) PBT resin, (B) PET resin, (C) polycarbonate (PC) resin, (D) impact modifier resin, optionally (E) styrene-acrylonitril (SAN) resin, (F) 4 to 60 parts by weight of (I) inorganic filler, based on 100 parts by weight of the resin mixture consisting of (F) ultra high molecular weight SAN resin, (G) main flame retardant, and (H) flame retardant aid, wherein the resin mixture comprises (A) PBT 25 to 93 weight% resin, (B) 1 to 40 weight% PET resin, (C) 1 to 40 weight% PC resin, (D) 1 to 40 weight% impact modifier resin, (E) 0 to 40 weight SAN resin A filler-reinforced PBT resin composition, comprising 0.1% to 10% by weight of (F) ultrahigh molecular weight SAN resin, 1.0 to 30% by weight of (G) flame retardant, and 0 to 10% by weight of (H) flame retardant aid. The filler-reinforced PBT resin composition according to claim 1, wherein the impact modifier resin (D) is an olefinic rubber copolymer, a styrene rubber copolymer or a polyester elastomer. The method of claim 2, wherein the polyester elastomer is a hard segment (polybutylene terephthalate) and the soft segment (soft segment) is used polytetramethylene oxide glycol, the polytetramethylene oxide glycol is a component A filler-reinforced PBT resin composition, characterized in that from 10 to 70% by weight weight ratio of the elastomer. The filler-reinforced PBT resin composition according to claim 1, wherein the ultra high molecular weight SAN resin (F) has a weight average molecular weight (M _w ) of 2,000,000 to 20,000,000. The filler-reinforced PBT resin composition according to claim 1, wherein the main flame retardant (G) is a brominated epoxy clock or a brominated polycarbonate-based compound. The filler-reinforced PBT resin composition according to claim 1, wherein the flame retardant aid (H) is antimony trioxide.