KR100513976B1 - Polyphenylene Sulfide Thermoplastic Resin Composition - Google Patents

Abstract

The polyphenylene sulfide-based thermoplastic resin composition according to the present invention comprises (A) 60 to 95 parts by weight of polyphenylene sulfide resin, (B) 5 to 40 parts by weight of polyphenylene ether resin, (C) the component (A) 1 to 5 parts by weight of an epoxy compound having 2-3 epoxy groups, and (D) 100 parts by weight of a base resin composed of the above-mentioned components (A) + (B), based on 100 parts by weight of a base resin composed of + (B). It is characterized by consisting of 20 to 250 parts by weight of the filler.

Description

Polyphenylene Sulfide Thermoplastic Resin Composition

Field of invention

The present invention relates to a polyphenylene sulfide thermoplastic resin composition. More specifically, the present invention relates to a polyphenylene sulfide thermoplastic resin composition having excellent mechanical strength and extrusion workability while minimizing the occurrence of burrs in an injection molding process.

Background of the Invention

In recent years, there is an increasing demand for thermoplastic resins having high heat resistance and good chemical resistance as materials for parts of electrical and electronic devices and parts of chemical devices. Conventionally, die casting metals such as aluminum and zinc have been used for precision parts such as optical parts and electrical and electronic parts, and these metal parts are being replaced by thermoplastic resins, especially reinforced plastics.

Such precision parts are required to have excellent physical properties such as heat resistance, flame retardancy, and workability, and polyphenylene sulfide has attracted attention as one of the thermoplastic resins that satisfy them. Polyphenylene sulfide is used as a material suitable for precision parts because of its excellent heat resistance, dimensional stability, chemical resistance, flame retardancy and processability. In particular, it is common to use inorganic fillers such as glass fibers of high content for high strength and dimensional stability.

However, polyphenylene sulfide has a problem in that burrs occur more than other resins during the molding process. The reason that many burrs are generated is because the shear rate dependency of polyphenylene sulfide is very small and the melt viscosity is still very low even in minute gaps such as parting lines of molds where shear rate is low during molding process, so that flow is easily Because it occurs.

For this reason, many studies have been conducted to minimize the occurrence of burrs of polyphenylene sulfide. Among the known techniques, there is a method of adding polyamide, which is not only sufficient to reduce the occurrence of burrs, but also has a problem in that the absorption of moisture due to the polyamide is increased to lower the dimensional stability.

Another known technique is a method of reducing the occurrence of burrs by adding polyphenylene ether resins, but in this case, it is effective to reduce burrs only by adding a considerable amount of polyphenylene ether. There is a disadvantage in that it is significantly reduced.

Japanese Patent Laid-Open No. 4-353561 discloses a resin composition in which polyphenylene sulfide (hereinafter referred to as "PPS") resin, a liquid crystalline polymer, and fibrous and / or particulate fillers having a specific melt viscosity are blended in a predetermined ratio. In Japanese Patent Laid-Open No. 3-197562, a resin composition comprising a linear PPS resin, a crosslinked PPS resin, a silane compound, and a fibrous filler is disclosed.

In addition, Japanese Patent Application Laid-open No. Hei 5-78576 has a filler in a heat-crosslinked PPS resin having a melt flow rate (MFR) of 3.5 g / 10 minutes or less and a base resin in which a MFR is mixed with a PPS resin of 150 g / 10 minutes or more. It discloses about the resin composition which mix | blended them. However, all of these techniques do not bring about the desired level of burr reduction effect.

In order to solve the above problems, the present inventors add an epoxy compound and a filler to a base resin composed of a thermoplastic polyphenylene sulfide resin and a polyphenylene ether resin, thereby minimizing the occurrence of burrs in the injection molding process, while maintaining mechanical strength. And polyphenylene sulfide thermoplastic resin composition excellent in extrusion workability.

An object of the present invention is to provide a polyphenylene sulfide thermoplastic resin composition which minimizes the occurrence of burrs during the injection molding process.

Another object of the present invention is to provide a polyphenylene sulfide thermoplastic resin composition having excellent mechanical strength.

Still another object of the present invention is to provide a polyphenylene sulfide thermoplastic resin composition having excellent extrusion workability while minimizing the occurrence of burrs during the injection molding process.

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

Summary of the Invention

The polyphenylene sulfide-based thermoplastic resin composition according to the present invention comprises (A) 60 to 95 parts by weight of polyphenylene sulfide resin, (B) 5 to 40 parts by weight of polyphenylene ether resin, (C) the component (A) 1 to 5 parts by weight of an epoxy compound having 2-3 epoxy groups, and (D) 100 parts by weight of a base resin composed of the above-mentioned components (A) + (B), based on 100 parts by weight of a base resin composed of + (B). It is characterized by consisting of 20 to 250 parts by weight of the filler.

Hereinafter, the content of the present invention will be described in detail.

Detailed Description of the Invention

(A) polyphenylene sulfide resin

The polyphenylene sulfide resin used in the thermoplastic resin composition according to the present invention is a resin containing 70 mol% or more of a unit having a structure of the following formula (1). It should contain 70 mol% or more of the repeating unit to obtain a high degree of crystallinity and excellent heat resistance, chemical resistance and strength.

[Formula 1]

The polyphenylene sulfide resin has a linear molecular structure having no branched or crosslinked structure or a molecular structure having branched or crosslinked structure depending on the production method thereof, and is not limited to having any one type of structure in the present invention.

An example of a typical method for producing a crosslinked polyphenylene sulfide resin is disclosed in Japanese Patent Laid-Open No. 45-3368, and a typical method for producing a linear polyphenylene sulfide resin is disclosed in Japanese Patent Laid-Open No. 52-11240.

In the polyphenylene sulfide resin of this invention, the copolymerization structural unit which has a structure of the following general formula may be included in content of less than 50 mol%, Preferably it is less than 30 mol%.

The polyphenylene sulfide resin (A) of the present invention preferably has a melt index in the range of 50 to 100 g / 10 min at a load of 2.16 kg at 316 ° C. in consideration of thermal stability and workability. If the melt index exceeds 300 g / 10 minutes, there is a problem of strength degradation, while if the melt index is less than 100 g / 10 minutes, problems of kneading and workability during the injection process occur.

The polyphenylene sulfide resin (A) in the present invention constitutes a base resin together with the following polyphenylene ether (B) and is used at 60 to 95 parts by weight.

(B) polyphenylene ether resin

Specific examples of the polyphenylene ether resin (B) used in the thermoplastic resin composition according to the present invention include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1, 4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl- 6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, Copolymers of poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether, and poly (2,6-dimethyl-1, Copolymers of 4-phenylene) ether and poly (2,3,5-triethyl-1,4-phenylene) ether. Among them, poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4 Preferred is a copolymer of -phenylene) ether, of which poly (2,6-dimethyl-1,4-phenylene) ether is most preferred.

Although the polymerization degree of the said polyphenylene ether resin (B) is not specifically limited, It is preferable that the intrinsic viscosity measured in 25 degreeC chloroform solvent is 0.2-0.8 in consideration of the thermal stability and workability of a resin composition.

In the present invention, the polyphenylene ether resin (B) together with the polyphenylene sulfide resin (A) constitutes a basic resin, and is used at 5 to 40 parts by weight. When used in excess of 40 parts by weight, mechanical strength and extrusion workability are reduced.

(C) Epoxy compound of 2-3 epoxy groups

The epoxy compound of 2-3 epoxy groups of this invention has a structure of following General formula (2).

[Formula 2]

Wherein R ₁ and R ₂ are each independently an aromatic compound having 6 to 8 carbon atoms, and the value of n is 0 or 1.

In the case of one epoxy group, there is almost no effect of reducing mechanical strength and burr, and in the case of four or more epoxy groups, the reaction proceeds abruptly, resulting in severe decrease in fluidity.

Specific examples of the epoxy compound having 2-3 epoxy groups of the present invention include a polyglycidyl ether compound, a polyglycidyl amine epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a resorcinol type epoxy compound, and tetrahydroxy. A bisphenol F-type epoxy compound, a cresol novolak-type epoxy compound, a phenol novolak-type epoxy compound, a cycloaliphatic epoxy compound, etc. are mentioned. In this invention, it is preferable to use bisphenol-A epoxy resin for the reduction effect of a burr, and the improvement of extrusion workability.

The content of the epoxy compound (C) having 2 to 3 epoxy groups used in the present invention is 1 to 5 parts by weight based on 100 parts by weight of the base resin consisting of the polyphenylene sulfide resin (A) and the polyphenylene ether (B). to be.

(D) filler

The filler used in the resin composition according to the present invention uses a fibrous filler, a particulate filler or a mixture thereof. Examples of fibrous fillers include glass fibers, carbon fibers, aramid fibers, potassium titanate fibers, silicon carbide fibers, Erstonaito and the like. Examples of the particulate filler include calcium carbonate, silica, titanium oxide, carbon black, alumina, lithium carbonate, iron oxide, molybdenum disulfide, graphite, glass beads, talc, clay mica, zirconium oxide, calcium silicate, boron nitride, and the like. .

The content of the fibrous filler, the particulate filler or the mixture (D) thereof used in the present invention is 20 to 250 with respect to 100 parts by weight of the base resin composed of the polyphenylene sulfide resin (A) and polyphenylene ether (B). Parts by weight.

In addition to the above components, coloring agents such as antioxidants, mold release agents, flame retardants, lubricants, pigments, dyes, small amounts of various polymers, and the like may be appropriately used in the thermoplastic resin composition of the present invention.

The polyphenylene sulfide thermoplastic resin composition of this invention can be manufactured by the well-known method of manufacturing a general resin composition. For example, the components of the present invention and other additives may be mixed simultaneously, then melt extruded in an extruder and made into pellets.

The thermoplastic resin composition according to the present invention can be used for molding a variety of products, in particular, while minimizing the occurrence of burrs during the molding process while maintaining excellent mechanical strength, processability and dimensional stability, excellent extrusion workability and electrical and electronic It can be applied to optical parts such as precision parts and optical pickup.

The present invention will be further illustrated by the following examples, which are merely illustrative of the present invention and are not intended to limit or limit the scope of the present invention.

Example

The specifications of (A) polyphenylene sulfide resin, (B) polyphenylene ether resin, (C) epoxy group of 2-3 epoxy groups and (D) filler used in the Example and the comparative example are as follows.

(A) polyphenylene sulfide resin

PPS of Japan DIC Co., Ltd., which had a melt index of 50-100 g / 10min at a load of 2.16 kg at 316 ° C, was used.

(B) polyphenylene ether resin

P-402 (brand name) which is a poly (2, 6- dimethyl- 1, 4- phenylene) ether of Asahi Kasei of Japan was used. The size of the resin particles was used in the form of a powder having an average particle diameter of several tens of ㎛.

(C) Epoxy compound of 2-3 epoxy groups

ERL-4221 (trade name) of Union Carbide, USA was used as compound (c ₁ ) having two epoxy groups. Further, the epoxy group with three compound (c ₂₎ was used as a EOCN-104S manufactured by Nippon's go Japanese ku (Nippon Kayaku).

(D) filler

(d ₁ ) fibrous filler

A glass fiber treated with a coupling agent such as silane and metaoxy silane, a lubricant, and a binding agent was used, which was 13 μm in diameter, Owens Corning Co., Ltd., and 13 mm in diameter.

(d ₂ ) particulate filler

Calcium carbonate used in the embodiment of the present invention used KRISTON-SS, a product of Korea Donghwa Material. The particle size used was an average particle diameter of 1.7 mu m.

In Examples and Comparative Examples of the present invention, a fibrous filler (d ₁ ) and a particulate filler (d ₂ ) were mixed and used.

Examples 1-4

The resin composition was prepared according to the composition shown in Table 1 using the above-mentioned components. The unit is parts by weight. After mixing each component, antioxidants and heat stabilizers were added, mixed in a conventional mixer, and extruded by feeding into a twin screw extruder having a screw L / D of 35 and a Φ value of 45 mm. Extruded through the extruder was prepared in pellet form, and then a specimen for measuring the physical properties and burr evaluation at the injection temperature of 320 ℃ was prepared using a 10 oz injection machine.

The physical properties of the specimens were measured at 23 ° C. and 50% relative humidity for 48 hours, and then the following physical properties were measured according to ASTM specifications. Physical property measurement results are shown in Table 1 below.

(1) Izod impact strength

Izod notch impact strength (1/8 ") was measured according to ASTM D-256, and the unit is kgf · cm / cm.

(2) flexural strength

Flexural strength was measured according to ASTM D-790 and the unit is kgf / cm 2.

(3) Burr occurrence degree

The degree of burr generation was evaluated by measuring the length of burr generated under the same injection conditions in a specific mold. The unit of measurement is mm.

Comparative Examples 1 to 4

In Comparative Example 1, polyphenylene sulfide resin was used alone as a base resin, and a specimen was prepared without using an epoxy compound (C) having 2-3 epoxy groups.

In Comparative Example 2, a specimen was prepared without using an epoxy compound (C) having 2-3 epoxy groups.

In Comparative Example 3, polyphenylene sulfide resin was used alone as a base resin, and a specimen was prepared using an epoxy compound (c ₂ ) having three epoxy groups.

In Comparative Example 4, a specimen was prepared of polyphenylene ether resin (B) in the constituents of the basic resin beyond the scope of the present invention. At this time, an epoxy compound (c ₂ ) having three epoxy groups was used.

Other measurement methods, measurement physical properties, conditions, and the like were performed under the same conditions as in Examples 1 to 3. The measurement results of the physical properties are shown in Table 1.

Example Comparative Example One 2 3 4 5 6 One 2 3 4 (A) polyphenylene sulfide resin 80 80 80 80 95 70 100 70 100 50 (B) polyphenylene ether resin 20 20 20 20 5 30 - 30 - 50 (C) a compound having an epoxy group (c ₁ ) 2.0 - - - - - - - - - (c ₂ ) - 0.5 2.0 3.0 2.0 2.0 - - 2.0 2.0 (D) filler (d ₁ ) 100 100 100 100 100 100 100 100 100 100 (d ₂ ) 85 85 85 85 85 85 85 85 85 85 Extrusion Production Yield (%) 95 90 95 96 96 95 95 60 95 80 Izod impact strength (kgfcm / cm) 7 6 8 8 7 8 6 5 6 4 Flexural strength (kgf / ㎠) 2,000 1,800 2,200 2,150 1,900 2,200 1,500 1,300 1,500 1,100 Burr length (mm) 0.2 0.2 0.15 0.1 0.3 0.05 3 0.1 2.7 0.2

From the results of Table 1, it can be seen that the polyphenylene sulfide thermoplastic resin composition according to the present invention not only has excellent mechanical strength and extrusion workability, but also can reduce the occurrence of burrs during the injection molding process.

The present invention has the effect of providing the polyphenylene sulfide thermoplastic resin composition which is excellent in mechanical strength and extrusion workability and minimized the occurrence of burrs during the injection molding process.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.

Claims (7)

(A) 60 to 95 parts by weight of polyphenylene sulfide resin; (B) 5 to 40 parts by weight of polyphenylene ether resin; (C) 1 to 5 parts by weight of an epoxy compound having 2 to 3 epoxy groups represented by the following formula (2) based on 100 parts by weight of the base resin consisting of the above-mentioned components (A) + (B); And [Formula 2] Wherein R ₁ and R ₂ are each independently an aromatic compound having 6 to 8 carbon atoms, and the value of n is 0 or 1. (D) 20 to 250 parts by weight of a filler based on 100 parts by weight of the base resin consisting of the above components (A) + (B); Polyphenylene sulfide thermoplastic resin composition, characterized in that consisting of. The polyphenylene sulfide thermoplastic resin composition according to claim 1, wherein the polyphenylene sulfide resin (A) has a melt index in the range of 50 to 100 g / 10 minutes at a load of 2.16 kg at 316 ° C. The epoxy compound (C) having 2 to 3 epoxy groups is a polyglycidyl ether compound, a polyglycidyl amine epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a resorcinol type epoxy compound. A polyphenylene sulfide thermoplastic resin composition selected from the group consisting of a tetrahydroxybisphenol F-type epoxy compound, a cresol novolak-type epoxy compound, a phenol novolak-type epoxy compound, and a cycloaliphatic epoxy compound. The polyphenylene sulfide thermoplastic resin composition according to claim 1, wherein the filler (D) is a fibrous filler, a particulate filler or a mixture thereof. The polyphenylene sulfide thermoplastic resin composition according to claim 4, wherein the fibrous filler is selected from the group consisting of glass fibers, carbon fibers, aramid fibers, potassium titanate fibers, silicon carbide fibers, and aerostonite. The method of claim 4, wherein the particulate filler is calcium carbonate, silica, titanium oxide, carbon black, alumina, lithium carbonate, iron oxide, molybdenum disulfide, graphite, glass beads, talc, clay mica, zirconium oxide, calcium silicate, and nitride Polyphenylene sulfide thermoplastic resin composition, characterized in that selected from the group consisting of boron. Molded article prepared from the polyphenylene sulfide thermoplastic resin composition of claim 1.