KR20180101854A - Polyarylene sulfide resin composition - Google Patents

Abstract

The present invention provides a polyarylene sulfide resin composition capable of representing improved metal adhesive characteristics while maintaining excellent mechanical characteristics and suppressing occurrence of outgas and burr or flash. The polyarylene sulfide resin composition comprises: 20 to 35 wt% of a polyarylene sulfide resin; 0.1 to 10 wt% of a polyarylene ether resin; 0.1 to 5 wt% of aluminosilicate; and 60 to 75 wt% of a filler material.

Description

[0001] POLYARYLENE SULFIDE RESIN COMPOSITION [0002]

The present invention relates to a polyarylene sulfide resin composition which is capable of exhibiting improved metal bonding properties while maintaining excellent mechanical properties while suppressing outgassing and barley generation.

Polyarylene sulfide (PAS), which is represented by polyphenylene sulfide (PPS), is widely used in automobiles, electrical and electronic products, machinery and the like due to its excellent strength, heat resistance, Has been widely used as a substitute for the same die casting metal.

On the other hand, PPS can have various flow properties through controlling the molecular weight and molecular weight distribution in the polymerization process, but a large amount of out gas is generated at the tip of the injection flow when adhering to metal due to low molecular weight oligomer or the like . Accordingly, there is a problem that metal adhesion is deteriorated due to failure to fill the fine pores of the metal surface when manufacturing parts requiring a process of bonding the PPS molded article and the metal with the metal insert part or the adhesive.

In addition, polyphenylene sulfide having high flowability has a very small melt viscosity dependency on shear rate. Therefore, when a molded article requiring high precision such as computer parts and connectors is manufactured using the same, The flow of the melt index is liable to occur in the fine gap portion of each component constituting the mold such as the contact surface particles, the projecting pin, and the pressed surface of the slide. As a result, a burr or flash is generated in the molded article.

Accordingly, there is a need to develop a PPS composition having excellent adhesion to metals while minimizing the amount of outgassing and generation of outgas generated at the flow front end, which is a fundamental problem of conventional metal bonding plastics.

Japanese Patent Application Laid-Open No. 1991-197562 U.S. Patent No. 2,513,188

An object of the present invention is to provide a polyarylene sulfide resin composition which is inhibited from the generation of outgas and bari, and which exhibits excellent mechanical properties and metal adhesion properties.

The present invention also provides a molded article produced using the resin composition.

According to an embodiment of the present invention,

20 to 35% by weight of a polyarylene sulfide resin;

0.1 to 10% by weight of a polyarylene ether resin;

0.1 to 5% by weight of aluminosilicate; And

60 to 75% by weight filler material,

Wherein the filler material comprises a fibrous filler and a particulate filler in a weight ratio of 1.5: 1 to 2.5: 1.

Specifically, in the polyarylene sulfide resin composition, the polyarylene sulfide resin may be a polyphenylene sulfide resin having a melt index of 500 to 1,000 g / min measured at 315 ° C / 5 kg according to ASTM D1238 have.

In the polyarylene sulfide resin composition, the polyarylene sulfide resin may be a linear polymer resin.

In the polyarylene sulfide resin composition, the polyarylene ether resin preferably has a weight average molecular weight of 20,000 to 40,000 g / mol, a viscosity of 0.3 to 0.45 dl / g, and a density of 1.02 to 1.1 g / cm ³ .

Specifically, the polyarylene ether resin is selected from the group consisting of poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6- Ether), poly (2-methyl-6-propyl-1, 4-phenylene) ether , Poly (2-ethyl-6-propyl-1,4-phenylene) ether, and copolymers thereof.

In the polyarylene sulfide resin composition, the fibrous filler may be a glass fiber having an aspect ratio of more than 1, more specifically, a glass fiber having a fiber diameter of 10 to 15 탆, a length of 1 to 10 mm It can be glass fiber.

The granular filler may have an average particle diameter (D ₅₀ ) of 3 to 10 μm, and may be specifically calcium carbonate.

At least one of the fibrous filler and the particulate filler is a compound selected from the group consisting of an epoxy resin, an acrylic resin, a urethane resin, a coupling agent, a lubricant, a fatty acid, a fatty acid ester, Can be surface-treated.

In the polyarylene sulfide resin composition, the aluminosilicate may have a number average particle diameter of 1 to 30 占 퐉 and a bulk density of 0.30 to 0.60 g / ml. Specifically, the aluminosilicate may be calcium aluminosilicate have.

The polyarylene sulfide resin composition may further comprise at least one additive selected from the group consisting of a coupling agent, an antioxidant, a lubricant, a pigment, a light stabilizer, a UV stabilizer, a plasticizer, a foaming agent, .

According to another embodiment of the present invention, there is provided a molded article produced from the polyarylene sulfide resin composition described above.

The polyarylene sulfide resin composition according to the present invention is capable of exhibiting excellent metal bonding characteristics while suppressing the generation of outgassing and barriers while maintaining excellent mechanical properties. Accordingly, the present invention can be useful for the production of molded articles for substitution of metal in automobiles, electric / electronic products or machinery, particularly for the production of molded articles requiring high precision or thin thickness such as computer parts or connectors.

Hereinafter, a supported catalyst according to a specific embodiment of the present invention and a method for producing an olefin polymer using the supported catalyst will be described.

According to one embodiment of the invention,

20 to 35% by weight of a polyarylene sulfide resin;

0.1 to 10% by weight of a polyarylene ether resin;

0.1 to 5% by weight of aluminosilicate; And

60 to 75% by weight filler material,

Wherein the filler material comprises a fibrous filler and a particulate filler in a weight ratio of 1.5: 1 to 2.5: 1.

The polyarylene sulfide resin composition contains an aluminosilicate and a polyarylene ether resin. By optimizing the kind and content of the constituent components in accordance therewith, the polyarylene sulfide resin composition can suppress the generation of outgas and barriers while maintaining excellent mechanical properties, Adhesive properties.

Further, in the polyarylene sulfide resin composition according to one embodiment of the present invention, the effect of the invention can be further improved by controlling the kind or physical properties of each constituent component. The following is a detailed description of each component.

(A) a polyarylene sulfide resin

The polyarylene sulfide resin has a structure in which an aromatic ring and a sulfur atom are bonded to each other as a repeating unit, and specifically includes a structure represented by the following formula (1) as a repeating unit:

[Chemical Formula 1]

In Formula 1, R ¹ and R ² are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, and an alkoxy group having 1 to 4 carbon atoms.

More specifically, when R ¹ and R ² in the general formula (1) are each a hydrogen atom, they can exhibit an excellent mechanical strength, and they can be bonded at a para position with a sulfur atom as shown in the following general formula (2) 3 can exhibit better mechanical strength than when bound at the sulfur atom and meta position.

(2)

(3)

Among them, particularly preferred is a structure in which the bond of the sulfur atom to the aromatic ring in the repeating unit is bonded at the para position as in the above formula (2) in view of the heat resistance and crystallinity of the polyarylene sulfide resin.

More specifically, the polyarylene sulfide resin may be a polyphenylene sulfide resin containing at least 70 mol%, more specifically at least 90 mol%, of the repeating unit represented by the formula (2).

The polyphenylene sulfide resin may be, for example, a linear molecular structure having no branching or crosslinking structure, or a molecular structure having branching or crosslinking.

The polyphenylene sulfide resin may further contain at least 30 mol% of at least one member selected from the group consisting of copolymer units having the following structure, more specifically 10 mol% The heat resistance and the mechanical strength of the phenol sulfide resin can be further improved.

The bonding method of the copolymer unit is not particularly limited, and may be either a random copolymer or a block copolymer.

In addition, the melt index (MI) of the polyarylene sulfide resin influences the workability of the resin composition. In the polyarylene sulfide resin composition according to one embodiment of the present invention, the polyarylene sulfide resin may have a melting point of 315 DEG C / min according to ASTM D1238. The melt index may be in the range of 500 to 1000 g / min, more specifically 700 to 850 g / min, more specifically 750 to 800 g / min, measured at 5 kg, So that a better processability improvement effect can be obtained.

The polyarylene sulfide resin may be contained in an amount of 20 to 35% by weight based on the total weight of the polyarylene sulfide resin composition. If it is contained in an amount of less than 20% by weight, there is a fear of deterioration of workability. If it exceeds 35% by weight, there is a fear of deterioration of mechanical properties. The polyarylene sulfide is preferably added in an amount of 25 to 35% by weight, more specifically 28 to 32% by weight, based on the total weight of the resin composition, considering the excellent processability and mechanical property improvement effect of the content control of the polyarylene sulfide resin . When it is included in the above-mentioned range, it exhibits more excellent workability and mechanical strength improvement effect and can be more suitable for injection molding.

(B) a polyarylene ether resin

The polyarylene ether resin serves to reduce the generation of bubbles.

Specifically, the polyarylene ether resin is selected from the group consisting of poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6- (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1, 4-phenylene) ether, or poly (2,6- , 6-trimethyl-1,4-phenylene) ether or a copolymer of poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6- Phenylene) ether, and the like, and any one or a mixture of two or more of them may be used.

Also, by controlling the physical properties such as the weight average molecular weight, viscosity, or density of the polyarylene ether resin, it is possible to further improve the mechanical properties of the polyarylene ether resin and the effect of inhibiting the formation of the polyarylene ether resin.

Specifically, the polyarylene ether resin may have a weight average molecular weight of 20,000 to 40,000 g / mol, more specifically 28,000 to 32,000 g / mol.

The viscosity of the polyarylene ether resin may be 0.3 to 0.45 dl / g, more specifically 0.36 to 0.40 dl / g.

The density of the polyarylene ether resin may be 1.02 to 1.1 g / cm ³ , more specifically 1.02 to 1.1 g / cm ³ .

When both of the above physical properties are satisfied, it is possible to exhibit a better anti-foaming effect.

The polyarylene ether resin may be contained in an amount of 0.1 to 10% by weight based on the total weight of the polyarylene sulfide resin composition. When the content of the polyarylene ether resin is less than 0.1% by weight, the effect of the polyarylene ether resin is less inhibited, and when it exceeds 10% by weight, the mechanical properties and workability of the resin composition may be deteriorated . Considering that the polyarylene ether resin has excellent barrier properties and mechanical properties and improvement of workability according to the control of the polyarylene ether resin content, the polyarylene ether resin is used in an amount of 1 to 10% by weight, more specifically 3 To 7% by weight. When the content is within the above range, the amount of bari is minimized, and the mechanical properties and processability can be well balanced.

(C) Filler

The filler improves the mechanical strength, dimensional stability (deformation or warping) and heat resistance of the polyarylene sulfide resin composition. Particularly, the length, diameter or diameter of the filler affects the dispersibility and wettability of the filler and, as a result, affects the mechanical properties and dimensional stability of the resin composition, and furthermore, the impact properties of the molded article. Accordingly, the above effect can be further improved by controlling the length, diameter, or diameter of the filler.

The polyarylene sulfide resin composition according to one embodiment of the present invention improves the dispersibility and wettability of the filler in the resin composition by incorporating the fibrous filler and the granular filler as a filler and as a result, Can be improved.

More specifically, the fibrous filler has a major axis length passing through the center of the filler and a center axis of the filler, wherein the aspect ratio of the minor axis perpendicular to the major axis is greater than 1, more specifically from 1 to 1500, 10 to 1000. By having a long shape in the longitudinal direction, the mechanical strength and dimensional stability (deformation or warpage) of the resin composition can be improved.

The fibrous filler may be specifically glass fiber, carbon fiber, aramid fiber, potassium titanate fiber or silicon carbide fiber, and any one or a mixture of two or more thereof may be used. Among these, in consideration of the remarkable effect of improving the mechanical strength and dimensional stability according to the use of the fibrous filler, the fibrous filler can be more specifically glass fiber in consideration of the chemical stability and the heat resistance improving effect of the resin composition.

The glass fibers may have a diameter of 10 to 15 탆, more specifically 10 to 13 탆. On the other hand, in the present invention, the diameter of the glass fiber means the average value of the major axis in the cross sections perpendicular to the long axis passing through the center of the glass fiber, and the cross-sectional shape of the glass fiber is not particularly limited , A round shape, an elliptical shape, or the like.

In addition, the glass fiber is used as chopped strands cut into a predetermined length in which a plurality of glass fibers are bundled. The length of the glass fiber used in the present invention is specifically 1 to 10 mm, more specifically, May be 3 to 4 mm.

It is possible to uniformly disperse in the resin composition when the fiber diameter and the length of the glass fiber satisfy both of the fiber diameter and the length of the glass fiber, thereby greatly improving the mechanical strength and dimensional stability (deformation or warpage) of the polyarylene sulfide resin composition. Accordingly, the filler may be a chopper glass fiber having a fiber diameter of 10 to 15 탆, more specifically 10 to 13 탆, and a length of 1 to 10 mm, more specifically, 3 to 4 mm.

The kind of the glass fiber is not particularly limited and may be A glass, C glass, E glass, or the like. E-glass (non-alkali glass) may be used in consideration of heat resistance and chemical stability of the resin composition.

On the other hand, the granular filler may be a filler having an aspect ratio of 1 or a filler having a spherical shape or the like having an aspect ratio of about 1.

The granular filler has a wider interface with the polyarylene sulfide than the fibrous filler due to its unique morphological characteristics, and as a result, can exhibit superior compatibility. More specifically, the average particle diameter of the particle filler may be 3 to 10 탆, more specifically 5 to 10 탆, in terms of the average particle diameter (D ₅₀ ). When having an average particle diameter within the above-mentioned range, the polyarylene sulfide resin exhibits superior compatibility with the resin composition without fear of breakage of the particle filler or deterioration of dispersibility due to agglomeration of the particle fillers, thereby improving the mechanical properties and dimensional stability Can be further improved.

On the other hand, in the present invention, the average particle diameter (D ₅₀ ) of the granular filler is measured as the volume average value D ₅₀ (that is, the particle diameter when the cumulative volume becomes 50%) in the particle size distribution measurement by the laser diffraction method Value.

The granular filler may be mineral fillers such as calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, clay, pyrophyllite, bentonite, sericite, zeolite, mica, mica, talc, Among these, calcium carbonate which can improve the mechanical properties, dimensional stability and heat resistance of the molded product to improve the impact properties can be used. More specifically, the calcium carbonate can be a heavy calcium carbonate, precipitated calcium carbonate (hard calcium carbonate, colloidal calcium carbonate ) And the like.

(Surface-treated calcium carbonate) surface-treated with a fatty acid, a fatty acid ester, a resin acid, a higher alcohol-added isocyanate compound, or the like.

In addition, since the inorganic filler has a simple adsorptive interaction with the polyarylene sulfide resin rather than a chemical bond, improvement in physical properties is limited. Accordingly, by chemically modifying the glass fiber surface through the surface treatment, a chemical bond is formed with the polyarylene sulfide resin to improve the dispersibility and the wettability of the surface, and as a result, the mechanical properties including the tensile strength of the resin composition are improved, The energy loss can be reduced and the dynamic characteristics can be improved. Specifically, at least one of the fibrous filler and the particulate filler may be an adhesive such as an epoxy resin, an acrylic resin or a urethane resin; Coupling agents such as epoxy silane and the like; Lubricant; A fatty acid, a fatty acid ester, a resin acid, a high-alcohol-added isocyanate compound, and the like. More specifically, in the case of the fibrous filler, it may be a urethane / epoxy silane surface treatment or urethane / aminosilane surface treatment, and in the case of the granular filler, a fatty acid, a fatty acid ester, a resin acid or a higher alcohol may have been surface treated with an isocyanate compound have.

The filler including the fibrous filler and the particulate filler may be contained in an amount of 60 to 75% by weight based on the total weight of the polyarylene sulfide resin composition. If the content of the filler is less than 60% by weight, the mechanical properties and dimensional stability improvement effect of the resin composition is insignificant, and as a result, the impact characteristics of the molded article may be deteriorated. If it exceeds 75% by weight, the processability of the resin composition may deteriorate. The filling material may be contained in an amount of 60 to 65% by weight in consideration of improvement in mechanical strength and dimensional stability of the polyarylene resin composition depending on the use of the filler and good balance of workability.

The fibrous filler and the particulate filler may be contained in a weight ratio of 1.5: 1 to 2.5: 1 under the condition that the content range of the filler is satisfied. If the mixing ratio of the granular filler in the fibrous filler exceeds the above range and the content of the fibrous filler is excessively large, the effect of improving the compatibility with the polyarylene sulfide resin may not be sufficient due to the relative reduction of the granular filler content, If the content is excessively large, the mechanical properties and dimensional stability improvement effect of the resin composition may not be sufficient due to the relative decrease in the content of the fibrous filler. Considering the remarkable improvement effect by controlling the mixing ratio of the fibrous filler and the granular filler, it can be mixed at a weight ratio of 2.25: 1 to 2.5: 1 more specifically.

(D) Aluminosilicate

The polyarylene sulfide resin composition according to an embodiment of the present invention may further include an aluminosilicate compound.

The aluminosilicate includes three-dimensional pores, which are also referred to as molecular sieves because of the size selectivity or shape selectivity of the molecules received into the pores. In detail, since silicon and aluminum form the framework of aluminosilicate, and the place where aluminum exists has a negative charge, positive ions for charge cancellation exist in the pore, and the remaining space in the pore is usually water molecules It is. At this time, some or all of the silicon or aluminum constituting the skeleton of the aluminosilicate may be substituted with a metal element such as Ba, Na, Ti, Mn, Co, Fe or Zn.

Such an aluminosilicate can exhibit an effect of suppressing outgassing.

The aluminosilicates usable in the present invention may specifically be metal-aluminosilicates such as calcium aluminosilicate, barium aluminosilicate, or sodium aluminosilicate, and any one or a mixture of two or more thereof may be used .

Moreover, the aluminosilicate has a particulate phase, and the particle size and the like may affect the outgassing suppression described above. Specifically, the aluminosilicate usable in the present invention may have a number average particle diameter of 1 to 30 mu m, more specifically 1 to 15 mu m. When the particle diameter is within the above-mentioned range, it exhibits an optimal specific surface area, thereby exhibiting excellent dispersibility and compatibility with the polyarylene sulfide resin. As a result, it is possible to exhibit a better outgas generation inhibiting effect.

In the present invention, the number average particle diameter can be measured by a laser diffraction scattering method.

In addition, the aluminosilicate may have a bulk density of 0.30 to 0.60 g / ml, more specifically 0.35 to 0.50 g / ml. When the above-mentioned number average particle size and the bulk density range are satisfied, the outgas generation suppressing effect can be further enhanced.

In the present invention, the bulk density of aluminosilicate can be measured by a weight measuring method corresponding to a certain volume. Specifically, it can be calculated by filling the measuring cylinder with aluminosilicate and measuring its weight, and dividing the measured weight by the volume of the measuring cylinder.

The aluminosilicate may be contained in an amount of 0.1 to 5% by weight based on the total weight of the polyarylene resin composition. When the content of the aluminosilicate is less than 0.1% by weight, the mechanical properties and dimensional stability improvement effects of the resin composition are insignificant, and as a result, the impact characteristics of the molded product may be deteriorated. If it exceeds 5% by weight, the processability of the resin composition may be deteriorated. Considering the suppression of the outgas generation according to the use of the aluminosilicate, the improvement of the mechanical strength and the dimensional stability of the polyarylene resin composition and the good balance of the workability, the aluminosilicate is more specifically contained in an amount of 1 to 3% by weight ≪ / RTI >

 (E) Other additives

The polyarylene sulfide resin composition according to one embodiment of the present invention may contain a coupling agent, an antioxidant, a lubricant, a colorant, a light stabilizer, a UV stabilizer, a plasticizer, a foaming agent, Flame retardant and the like may be further included.

For example, the coupling agent improves the dispersion and wettability of the filler and, as a result, improves the flashing property as well as mechanical properties such as strength and toughness of the resin composition. Specifically, the silane compound More specifically, it may contain an epoxy group-containing compound such as? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Silane compounds; isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ- An isocyanate group-containing silane compound such as propylethyldimethoxysilane,? -Isocyanatopropylethyldiethoxysilane and? -Isocyanatopropyltrichlorosilane; amino group-containing silane compounds such as? - (2-aminoethyl) aminopropylmethyldimethoxysilane,? - (2-aminoethyl) aminopropyltrimethoxysilane and? -aminopropyltrimethoxysilane; containing silane compounds such as? -hydroxypropyltrimethoxysilane,? -hydroxypropyltrimethoxysilane and? -hydroxypropyltriethoxysilane, and any one or a mixture of two or more of them may be used.

The coupling agent may be preliminarily treated with respect to the filler material, specifically, after the surface treatment, or may be used alone as an additive agent.

When the coupling agent is used in an excessive amount, injection molding may be difficult due to an increase in the melt viscosity of the resin composition. Therefore, in consideration of moldability, the 100% by weight of the polyarylene sulfide resin 0.1 to 10 parts by weight based on 100 parts by weight of the composition.

The antioxidant may exhibit an antioxidative effect such as improving the thermal stability of the resin composition. Examples of the antioxidant include phosphorus, phenolic, amine, or sulfur-based antioxidants. Examples of the phosphorus antioxidant include phosphoric acid ester such as triphenylphosphate (TPP), triethyl phosphate (TEP); Diethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, bis (2,6- Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, bis (2,4-ditbutylphenyl) pentaerythritol diphosphite bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphate, bis (2,4-dicumylphenyl) pentaerythritol-diphosphite, or distearyl pentaerythritol diphosphate Phosphonates such as distearyl penta erythritol diphosphate; Phosphinate; Phosphine oxide; Phosphazene; Or metal salts thereof, and any one or a mixture of two or more of them may be used.

Examples of the phenolic antioxidant include tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene bis [3- Di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3,5- Propionamide], and any one or a mixture of two or more of them may be used

The antioxidant may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyarylene sulfide resin, because excessive use of the antioxidant may result in gasification during melt-kneading or injection molding to deteriorate the working environment.

The lubricant enhances moldability to prevent friction between the polyarylene sulfide resin composition and the metal of the mold and to provide releasability during desorption in the mold. Specifically, the lubricant may be an olefin wax, Wax, montanic ester wax and the like can be used.

If the lubricant is contained in an excessive amount, there is a fear of lowering the moldability. Therefore, it may be contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyarylene sulfide resin.

As the coloring agent, various conventional organic or inorganic pigments known in the art can be used. Specifically, titanium dioxide (TiO ₂ ), carbon black and the like can be given. Of these, carbon black can be used. The colorant may be contained in an amount of 0.1 to 10% by weight, more specifically 0.3 to 7% by weight, based on the total weight of the resin composition, taking into consideration the haze characteristics and the mechanical properties of the polyarylene sulfide resin composition.

In addition, the polyarylene sulfide resin composition may contain at least one selected from the group consisting of polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyether sulfone, polyetheretherketone, polyether A synthetic resin such as a polyolefin-based rubber, a polyurethane-based rubber, a polyolefin-based rubber, a polyolefin-based rubber, a polypropylene-based resin, Fluorine rubber, silicone rubber, and the like.

As described above, the polyarylene sulfide resin composition according to one embodiment of the present invention comprises 20 to 35% by weight of a polyarylene sulfide resin; 0.1 to 10% by weight of a polyarylene ether resin; 0.1 to 5% by weight of aluminosilicate; And 60 to 75% by weight of a filler, and optionally 0.1 to 10% by weight of at least one other additive, wherein the filler comprises a fibrous filler and a particulate filler in a weight ratio of 1.5: 1 to 2.5: 1, More specifically, in a weight ratio of 2.25: 1 to 2.5: 1, outgas and barley can be suppressed while maintaining excellent mechanical properties, and excellent adhesion properties can be exhibited.

More specifically, the polyarylene sulfide resin composition comprises 25 to 35% by weight of a polyarylene sulfide resin; 1 to 10% by weight of a polyarylene ether resin; 1 to 3% by weight of aluminosilicate; And 60 to 65% by weight of a filler, and optionally 0.1 to 10% by weight of at least one other additive, wherein the filler comprises a fibrous filler and a particulate filler in a weight ratio of 1.5: 1 to 2.5: 1, More specifically, in a weight ratio of 2.25: 1 to 2.5: 1, the above effects can be further improved by optimizing the contents of the components.

The polyarylene sulfide resin composition according to one embodiment of the present invention having the above composition may be prepared by mixing a polyarylene sulfide resin, a polyarylene ether resin, a fibrous filler, a granular filler, and optionally other additives, And then melt-kneading.

The mixing process may be performed using a conventional mixing apparatus such as a ribbon blender, Henschel mixer, V blender, and the like.

The melt-kneading may be performed using a single-screw extruder, a biaxial extruder, a Banbury mixer, a mixing roll, or a kneader, and more specifically, to provide a shearing force for improving the dispersibility of various additives during melt- Which can be carried out using a twin-screw extruder.

The polyarylene sulfide resin composition according to one embodiment of the present invention as described above comprises a fibrous filler and a granular filler together with a polyarylene ether resin, and further, the content of the constituent components containing them is optimized Whereby generation of burrs is suppressed, and excellent mechanical properties and metal bonding properties can be exhibited.

Specifically, the resin composition may have a Notched Izod Impact Strength of 50 J / m or more, more specifically 50 to 70 J / m, measured according to ASTM D256 using a 1/8 "specimen.

The resin composition may have a tensile strength of 150 MPa or more, more specifically 150 to 180 MPa, measured at a speed of 5 mm / min according to ASTM D638.

The resin composition had a flexural strength measured at a speed of 5 mm / min according to ASTM D790 of 230 MPa Or more, and more specifically, 230 to 250 MPa.

The resin composition may have a metal adhesive strength of 190 MPa or more, more specifically 190 to 220 MPa.

The resin composition may have a spiral test (barrel temperature: 310 ° C) of 0.06 g or less.

The resin composition may have an outgassing amount of 200 cc or less, more specifically 150 cc or less.

As described above, the polyarylene sulfide resin composition according to one embodiment of the present invention has excellent mechanical properties, and can be molded into a variety of molded parts, such as unstretched, unstretched, etc., by injection molding, injection compression molding, blow molding or extrusion molding. Sheet, fiber, or pipe, such as an extruded sheet, a drawn sheet, a drawn sheet, a drawn sheet, a drawn sheet, a drawn sheet, a drawn sheet, a drawn sheet,

Accordingly, another embodiment of the present invention provides a molded article produced using the polyarylene sulfide resin composition.

The molded article can be widely used in various automobiles, electric / electronic products, or machine parts. In particular, since the generation of outgas and the generation of outgassing are suppressed with excellent mechanical properties and excellent metal bonding properties, Or a connector requiring high precision or a thin thickness.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. However, this is provided as an example of the invention, and the scope of the invention is not limited thereto in any sense.

The polyphenylene sulfide, filler, coupling agent, antioxidant, lubricant and other additives used in Examples and Comparative Examples are as follows.

(A1) Polyphenylene sulfide (PPS)

A linear polyphenylene sulfide resin having a melt index of 500 to 1000 g / min (measured at 315 DEG C / 5 kg in accordance with ASTM D1238) and having a Tm of 280 DEG C was used.

(A2) Polyphenylene sulfide (PPS)

A cross-linked polyphenylene sulfide resin having a melt index of 500 to 1000 g / min (measured at 315 DEG C / 5 kg in accordance with ASTM D1238) and having a Tm of 280 DEG C was used

(B) a polyarylene ether

(2,6-dimethyl-1,4-phenylene) ether resin having a weight average molecular weight of 31,800 g / mol, a density of 1.06 g / cm ³ and a viscosity of 0.38 ± 0.02 dl / g was used.

(C1) fibrous filler

Glass fibers having a fiber diameter of 10 to 13 μm and a chop length of 3 to 4 mm and having been surface-treated with an epoxy silane.

(C2) granular filler

Spherical calcium carbonate having an average particle diameter (D ₅₀ ) of 5.5 μm was used.

(D) Aluminosilicate

Calcium aluminosilicate having a number average particle diameter of 2.5 mu m and a bulk density of 0.43 g / mL was used.

[Examples 1 and 2 and Comparative Examples 1 to 8]

The above components were mixed in the compositions shown in the following table, and then melt-kneaded at 300 to 330 ° C. using a twin-screw extruder having a screw L / D of 42 and a Φ value of 40 mm to prepare a resin composition in the form of pellets Respectively.

The pellet-shaped resin composition thus prepared was dried at 120 ° C. for 3 hours or more, and then ASTM specimens were injection-molded at an injection temperature of 320 ° C. and a mold temperature of 120 ° C. for 48 hours at an ambient temperature of 23 ° C. and a relative humidity of 60% .

Constituent Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Example 1 Example 2 PPS (A1) - 35 35 - 32 32 30 28 31 30 PPS (A2) 35 - - 32 - - - - - - The polyarylene ether (B) - - - 3 3 3 5 7 3 3 Fibrous filler
(C1) 35 35 45 30 30 45 45 45 45 45 The granular filler (C2) 30 30 20 35 35 20 20 20 20 20 The aluminosilicate (D) - - - - - - - - One 2

In Table 1, the content of each component is in terms of wt%

[Test Example]

The physical properties of the polyphenylene sulfide resin composition specimens prepared in Examples 1 and 2 and Comparative Examples 1 to 8 were measured by the following methods, and the results are shown in Table 2 below.

Tensile strength: Measured according to ASTM D638 using a specimen. The crosshead speed of the tensile tester was measured at 5 mm / min.

Flexural Strength: Measured according to ASTM D790, where the crosshead speed of the tensile tester was measured at 1.3 mm / min.

Notched Izod Impact Strength: Measured according to ASTM D256 using 1/8 "specimens.

Bar size: 12.7 x 127 x 3 mm The thin section cut into the gas vent molds of different sizes was cut at the end of the specimen, and the weight of the cut section was measured.

The amount of outgassing was measured by P & T-GC / MS at 320 ° C for 10 minutes.

Adhesion property: A zinc plate having a size of 0.8 x 0.8 cm was fixed to the specimen, and the denatured acrylic adhesive was evenly applied to the specimen. The adhesive strength of the glued specimens was measured using a flexural tester at maximum force until the zinc plate adhered to the specimen was broken.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Example 1 Example 2 Barley production
(g) 0.15 0.14 0.1 0.09 0.1 0.05 0.05 0.04 0.05 0.06 Metal adhesion
(MPa) 175 190 191 179 192 195 192 179 201 193 Outgas volume
(cc) 870 350 290 950 410 340 340 380 150 134 Chlorine content
(cc) 850 740 690 800 670 660 645 650 645 650 The tensile strength
(Mpa) 140 155 160 135 152 157 152 148 157 153 Flexural strength
(MPa) 210 235 240 205 232 236 232 225 235 230 Impact strength
(J / m) 55 55 60 50 53 55 51 45 56 54

As a result of the experiment, in Examples 1 and 2 in which calcium aluminosilicate was added, the outgassing amount was remarkably reduced in the light of Comparative Examples 1 to 8, and as a result, the metal adhesion was greatly increased.

In addition, the inclusion of the fibrous filler mixed with the polyarylene ether resin at the optimum mixing ratio and the granular filler significantly reduced the amount of burrs while maintaining excellent mechanical properties.

 From these results, it can be seen that the polyarylene sulfide resin composition according to the present invention exhibits improved metal bonding properties while suppressing the generation of outgas and barriers while maintaining excellent mechanical properties, It can be seen that the present invention can be useful for the production of a substitute metal replacement product, particularly for the production of a molded article requiring a high precision or a thin thickness.

Claims (14)

20 to 35% by weight of a polyarylene sulfide resin;
0.1 to 10% by weight of a polyarylene ether resin;
0.1 to 5% by weight of aluminosilicate; And
60 to 75% by weight filler material,
Wherein the filler comprises a fibrous filler and a particulate filler in a weight ratio of 1.5: 1 to 2.5: 1.
The method according to claim 1,
Wherein the polyarylene sulfide resin is a polyphenylene sulfide resin composition having a melt index of 500 to 1,000 g / min measured at 315 DEG C / 5 kg according to ASTM D1238.
The method according to claim 1,
Wherein the polyarylene sulfide resin is a linear polymer resin.
The method according to claim 1,
The polyarylene ether resin has a weight average molecular weight of from 20,000 to 40,000 g / mol, a viscosity of 0.3 to 0.45 dl / g, a density of 1.02 to 1.1 g / cm ³ a, polyarylene sulfide resin composition.
The method according to claim 1,
The polyarylene ether resin may be at least one selected from the group consisting of poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl- (2-methyl-6-ethyl-1,4-phenylene) ether, poly 2-ethyl-6-propyl-1,4-phenylene) ether, and copolymers thereof.
The method according to claim 1,
Wherein the fibrous filler is a glass fiber having an aspect ratio of more than 1.
The method according to claim 6,
Wherein the glass fiber has a fiber diameter of 10 to 15 占 퐉 and a length of 1 to 10 mm.
The method according to claim 1,
Wherein the particulate filler has an average particle diameter (D ₅₀ ) of 3 to 10 탆.
The method according to claim 1,
Wherein the particulate filler is calcium carbonate.
The method according to claim 1,
Wherein at least one of the fibrous filler and the particulate filler is a compound selected from the group consisting of an epoxy resin, an acrylic resin, a urethane resin, a coupling agent, a lubricant, a fatty acid, a fatty acid ester, By weight of the polyarylene sulfide resin composition.
The method according to claim 1,
Wherein the aluminosilicate has a number average particle diameter of 1 to 30 占 퐉 and a bulk density of 0.30 to 0.60 g / ml.
The method according to claim 1,
Wherein the aluminosilicate is calcium aluminosilicate.
The method according to claim 1,
Wherein the polyarylene sulfide resin composition further comprises any one or two or more additives selected from the group consisting of a coupling agent, an antioxidant, a lubricant, a pigment, a light stabilizer, a UV stabilizer, a plasticizer, a foaming agent, an antirust agent and a flame retardant.
A molded article produced from the polyarylene sulfide resin composition according to claim 1.