KR102201207B1 - Polyarylene sulfide resin composition - Google Patents

Abstract

In the present invention, there is provided a polyarylene sulfide resin composition capable of exhibiting improved metal adhesion properties by suppressing outgassing and barrier generation while maintaining excellent mechanical properties.

Description

Polyarylene sulfide resin composition TECHNICAL FIELD [POLYARYLENE SULFIDE RESIN COMPOSITION}

The present invention relates to a polyarylene sulfide resin composition capable of exhibiting improved metal adhesion properties by suppressing outgassing and barrier generation while maintaining excellent mechanical properties.

Polyarylene sulfide (PAS), represented by polyphenylene sulfide (PPS), has excellent strength, heat resistance, flame retardancy, and workability, so it can be used in automobiles, electrical/electronic products, machinery, etc. It is widely used as a material replacing the same die casting metal.

On the other hand, PPS can have various flow properties by 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 bonding with metal due to low molecular weight oligomers. . For this reason, when manufacturing a part requiring a process of bonding a PPS molded product and a metal with a metal insert or an adhesive, there is a problem in that metal adhesion is deteriorated because microscopic voids on the metal surface cannot be filled.

In addition, since polyphenylene sulfide with high flowability has a very small dependence on the shear rate of melt viscosity, when using it to produce molded products that require high precision, such as computer parts and connectors, molds with low shear rates during the molding process. The flow of the melt index was likely to occur in the minute gaps of each part constituting the mold, such as the particles of the joint surface of the joint, the protruding pin, and the pressing surface of the slide, and as a result, burr or flash occurred in the manufactured molded product.

Accordingly, there is a need to develop a PPS composition having excellent adhesion performance with metal while minimizing the amount of outgas and the occurrence of variance generated at the flow front, which is a fundamental problem of the conventional metal adhesive plastic.

Japanese Patent Publication No. 1991-197562 US Patent No. 2,513,188

An object of the present invention is to provide a polyarylene sulfide resin composition that suppresses outgassing and variability and exhibits excellent mechanical properties and metal adhesion properties.

In addition, the present invention is to provide a molded article manufactured by 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

Including 60 to 75% by weight of the filler,

The filler is provided with a polyarylene sulfide resin composition comprising a fibrous filler and a granular 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 under a condition of 315° C./5 kg according to ASTM D1238. have.

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

In addition, in the polyarylene sulfide resin composition, the polyarylene ether resin 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 I can.

Specifically, the polyarylene ether resin is 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 and a copolymer thereof may be one containing any one or two or more selected from the group consisting of.

In addition, in the polyarylene sulfide resin composition, the fibrous filler may be a glass fiber having an aspect ratio of more than 1, and the glass fiber has a fiber diameter of 10 to 15 μm, and a chop length of 1 to 10 mm. It may be chopped fiberglass.

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

In addition, at least one of the fibrous filler and granular filler is a compound selected from the group consisting of epoxy resins, acrylic resins, urethane resins, coupling agents, lubricants, fatty acids, fatty acid esters, resin acids, and higher alcohol-added isocyanate compounds. Can be surface treated.

In addition, in the polyarylene sulfide resin composition, the alumino silicate may have a number average particle diameter of 1 to 30 μm, a bulk density of 0.30 to 0.60 g/ml, and specifically calcium aluminosilicate. have.

In addition, 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, a rust inhibitor, and a flame retardant. I can.

In addition, according to another embodiment of the present invention, a molded article manufactured from the polyarylene sulfide resin composition is provided.

The polyarylene sulfide resin composition according to the present invention maintains excellent mechanical properties while suppressing outgassing and variability, thereby exhibiting excellent metal bonding properties. Accordingly, it may be useful for manufacturing a molded article for metal replacement in automobiles, electrical and electronic products, or machinery, particularly for manufacturing a molded article requiring high precision or thin thickness, such as a computer part or a connector.

Hereinafter, a supported catalyst according to a specific embodiment of the present invention and a method of preparing 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

Including 60 to 75% by weight of the filler,

The filler is provided with a polyarylene sulfide resin composition comprising a fibrous filler and a granular filler in a weight ratio of 1.5:1 to 2.5:1.

The polyarylene sulfide resin composition includes an alumino silicate and a polyarylene ether resin, and by optimizing the type and content of the constituents accordingly, excellent mechanical properties are maintained while outgassing and occurrence of barri are suppressed. It can exhibit adhesive properties.

Furthermore, in the polyarylene sulfide resin composition according to an embodiment of the present invention, the effect of the present invention may be further improved by controlling the type or physical properties of each component. Hereinafter, a detailed look at each component is as follows.

(A) polyarylene sulfide resin

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

[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, in Formula 1, when R ¹ and R ² are each a hydrogen atom, they may exhibit excellent mechanical strength, and further, as in Formula 2 below, bonded to a sulfur atom at a para position, or the following formula As shown in Fig. 3, when the sulfur atom is bonded to the meta position, it may exhibit better mechanical strength.

[Formula 2]

[Formula 3]

Among these, it is particularly preferable from the viewpoint of heat resistance and crystallinity of the polyarylene sulfide resin that the sulfur atom is bonded to the aromatic ring in the repeating unit at the para position as in the general formula (2).

More specifically, the polyarylene sulfide resin may be a polyphenylene sulfide resin including 70 mol% or more, more specifically 90 mol% or more of the repeating unit represented by Formula 2 above.

The polyphenylene sulfide resin may be, for example, a linear molecular structure having no branched or crosslinked structure, or may have a branched or crosslinked molecular structure.

In addition, the polyphenylene sulfide resin may further contain 30 mol% or less of at least one selected from the group consisting of copolymer units having the following structure, and more specifically, when further containing 10 mol% or less, polyaryl The heat resistance and mechanical strength of the rensulfide resin can be further improved.

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

Further, the melt index (MI) of the polyarylene sulfide resin affects the processability of the resin composition. Such MI can be adjusted through the control of the type of monomer, molecular weight, etc., in the polyarylene sulfide resin composition according to an embodiment of the present invention, the polyarylene sulfide resin is 315 °C / according to ASTM D1238 The melt index measured under the condition of 5 kg may be 500 to 1000 g/min, more specifically 700 to 850 g/min, even more specifically 750 to 800 g/min, and the melt index in the above range By having it, it can exhibit a more excellent processability improvement effect.

The polyarylene sulfide resin may be included in an amount of 20 to 35% by weight based on the total weight of the polyarylene sulfide resin composition. If the content is less than 20% by weight, there is a concern of deterioration in processability, and if it exceeds 35% by weight, there is a concern of decrease in mechanical properties. Considering the excellent effect of improving processability and mechanical properties according to the content control of the polyarylene sulfide resin, the polyarylene sulfide is 25 to 35% by weight, more specifically 28 to 32% by weight based on the total weight of the resin composition. Can be included. When included in the above range, it exhibits more excellent processability and mechanical strength improvement effect, and thus may be more suitable for injection molding.

(B) polyarylene ether resin

The polyarylene ether resin serves to reduce the occurrence of bari.

Specifically, the polyarylene ether resin is 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 or Polyphenylene ether, such as poly(2-ethyl-6-propyl-1,4-phenylene) ether, or poly(2,6-diphenyl-1,4-phenylene) ether and poly(2,3 ,6-trimethyl-1,4-phenylene) ether, or poly(2,6-dimethyl-1,4-phenylene) ether and poly(2,3,6-triethyl-1,4- It may be a copolymer of the polyphenylene ether, such as phenylene) ether, and any one or a mixture of two or more of them may be used.

In addition, it is possible to further improve the mechanical properties of the resin composition and the effect of suppressing the occurrence of barri by adding the polyarylene ether resin by controlling physical properties such as the weight average molecular weight, viscosity, or density of the polyarylene ether resin.

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

In addition, 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.

In addition, 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 all of the above-described physical properties are satisfied, the effect of suppressing the occurrence of bari may be more excellent.

The polyarylene ether resin may be included 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 suppressing barriness due to the use of the polyarylene ether resin is insignificant, and when it exceeds 10% by weight, the mechanical properties and processability of the resin composition may be deteriorated. . In consideration of the excellent effect of suppressing variability and improving mechanical properties and processability according to the control of the polyarylene ether resin content, the polyarylene ether resin is 1 to 10% by weight, more specifically 3, based on the total weight of the resin composition. It may be included in to 7% by weight. When included in the above content range, the amount of bari generated is minimized, and mechanical properties and processability can be well balanced.

(C) filler

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

The polyarylene sulfide resin composition according to an embodiment of the present invention includes a mixture of a fibrous filler and a granular filler as a filler, thereby improving the dispersibility and wettability of the filler in the resin composition, and as a result, mechanical properties and dimensional stability. Can be improved.

Specifically, the fibrous filler has an aspect ratio, which is the ratio of the length of the long axis passing through the center of the filler and the length of the minor axis perpendicular to the long axis, passing through the center of the filler material is greater than 1, more specifically 1 to 1500, more specifically From 10 to 1000, by having an elongated 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 specifically be glass fiber, carbon fiber, aramid fiber, potassium titanate fiber, silicon carbide fiber, and the like, and any one or a mixture of two or more of them may be used. Among these, the fibrous filler may be more specifically glass fiber when considering the remarkable effect of improving mechanical strength and dimensional stability according to the use of the fibrous filler, and the chemical stability and heat resistance of the resin composition.

In addition, the glass fiber may have a diameter of 10 to 15 μm, more specifically 10 to 13 μm. Meanwhile, in the present invention, the diameter of the glass fiber refers to the average value of the major diameters in cross sections perpendicular to the major axis passing through the center of the glass fiber, and at this time, the cross-sectional shape of the glass fiber is not particularly limited. , It may be in various shapes such as a round shape or an ellipse shape.

In addition, the glass fibers are used as chopped strands obtained by cutting a plurality of glass fibers into a predetermined length, and the chopped length of the chopped glass fibers usable in the present invention is specifically 1 to 10 mm, more specifically It may be 3 to 4mm.

When the fiber diameter condition of the glass fiber and the chop length condition are simultaneously satisfied, it is uniformly dispersed in the resin composition, and the mechanical strength and dimensional stability (deformation or warpage) of the polyarylene sulfide resin composition can be greatly improved. Accordingly, the filler may be a chop glass fiber having a fiber diameter of 10 to 15 μm, more specifically 10 to 13 μm, a length of 1 to 10 mm, and more specifically 3 to 4 mm.

The type of the glass fiber is not particularly limited, and may be A glass, C glass or E glass. Among these, it may be E glass (alkali-free glass) in consideration of the heat resistance and chemical stability of the resin composition.

Meanwhile, the granular filler may be a spherical filler having an aspect ratio of 1 or a spherical filler having an aspect ratio of about 1, or a filler having a similar shape.

The granular filler has a wider contact interface with polyarylene sulfide compared to the fibrous filler due to its peculiar morphological characteristics, and as a result, may exhibit better compatibility. More specifically, the average particle diameter (D ₅₀ ) of the particle filler may be 3 to 10 μm, more specifically 5 to 10 μm. When it has an average particle diameter within the above range, it exhibits more excellent compatibility with polyarylene sulfide resin without fear of destruction of the particle filler or decrease in dispersibility due to agglomeration of the particle fillers, thereby improving the mechanical properties and dimensional stability of the resin composition. It can be further improved.

Meanwhile, 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 laser light diffraction method. It is one value.

Specifically, 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, and the like, Among these, it may be calcium carbonate that can improve the impact properties of molded products by showing more excellent mechanical properties, dimensional stability and heat resistance improvement effects.More specifically, heavy calcium carbonate, precipitated calcium carbonate (hard calcium carbonate, colloidal calcium carbonate ), etc.

Calcium carbonate (surface-treated calcium carbonate) surface-treated with a fatty acid, fatty acid ester, resin acid, higher alcohol-added isocyanate compound, or the like can also be used.

In addition, since the filler, which is an inorganic material, undergoes a simple adsorptive interaction with a polyarylene sulfide resin rather than a chemical bond, there is a limitation in improving physical properties. Accordingly, by chemically modifying the surface of the glass fiber through surface treatment, a chemical bond is formed with the polyarylene sulfide resin to improve dispersibility and surface wettability, and as a result, mechanical properties including 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 granular filler may include an adhesive such as an epoxy resin, an acrylic resin, or a urethane resin; Coupling agents such as epoxysilane and the like; Lubricant; It may be surface-treated with fatty acids, fatty acid esters, resin acids, and higher alcohol-added isocyanate compounds. More specifically, in the case of a fibrous filler, it may be a urethane/epoxysilane surface treatment or a urethane/aminosilane surface treatment, and in the case of a granular filler, a fatty acid, fatty acid ester, resin acid, or higher alcohol addition may be surface-treated with an isocyanate compound. have.

The filler including the fibrous filler and the granular filler may be included 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 effect of improving the mechanical properties and dimensional stability of the resin composition is insignificant, and as a result, there is a concern that the impact properties of the molded article are deteriorated. In addition, when it exceeds 75% by weight, there is a concern that the processability of the resin composition is deteriorated. When considering the improvement of mechanical strength and dimensional stability of the polyarylene resin composition and good balance of processability according to the use of the filler, the filler may be included in an amount of 60 to 65% by weight more specifically.

In addition, under conditions that satisfy the content range of the filler, the fibrous filler and the granular filler may be included in a weight ratio of 1.5:1 to 2.5:1. If the mixing ratio of the granular filler of the fibrous filler is out of the above range and the content of the fibrous filler is too large, the effect of improving the compatibility with the polyarylene sulfide resin may not be sufficient due to the relative decrease of the granular filler content. If the content is too high, the effect of improving the mechanical properties and dimensional stability of the resin composition may not be sufficient due to a relative decrease in the content of the fibrous filler. Accordingly, when considering the remarkable improvement effect according to the control of the mixing ratio of the fibrous filler and the granular filler, more specifically, it may be mixed in a weight ratio of 2.25:1 to 2.5:1.

(D) aluminosilicate

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

The aluminosilicate includes three-dimensional pores, and is also referred to as a molecular sieve due to the size selectivity or shape selectivity of molecules that are accepted into the pores. In detail, since silicon and aluminum form the skeleton of aluminosilicate, and the site where aluminum is negatively charged, cations for charge offset exist in the pore, and the remaining space in the pore is usually re-used as water molecules. It is set. At this time, some or all of 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 aluminosilicate may exhibit an effect of suppressing outgassing.

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

In addition, the aluminosilicate has a particulate shape, and the particle size and the like may have an effect on the above-described suppression of outgassing. Specifically, the aluminosilicate usable in the present invention may have a number average particle diameter of 1 to 30 μm, more specifically 1 to 15 μm. In the case of having a particle diameter in the above range, excellent dispersibility and compatibility with the polyarylene sulfide resin are exhibited by showing an optimum specific surface area, and as a result, a more excellent effect of suppressing outgassing can be exhibited.

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

In addition, the alumino silicate may have a bulk density of 0.30 to 0.60 g/ml, more specifically 0.35 to 0.50 g/ml. When the bulk density range is satisfied in addition to the number average particle diameter described above, the effect of suppressing outgassing can be further enhanced.

In the present invention, the bulk density of the alumino silicate can be measured through a weight measurement method corresponding to a predetermined volume. Specifically, after filling the measuring cylinder with alumino silicate and measuring its weight, it can be calculated by dividing the measured weight by the volume of the measuring cylinder.

The alumino silicate as described above may be included in an amount of 0.1 to 5% by weight based on the total weight of the polyarylene resin composition. If the content of the alumino silicate is less than 0.1% by weight, the effect of improving mechanical properties and dimensional stability to the resin composition is insignificant, and as a result, there is a concern that the impact properties of the molded article are deteriorated. In addition, when it exceeds 5% by weight, there is a concern that the processability of the resin composition is deteriorated. In consideration of suppression of outgassing due to the use of alumino silicate, improvement of mechanical strength and dimensional stability of the polyarylene resin composition, and good balance of processability, the alumino silicate is more specifically in an amount of 1 to 3% by weight. Can be included as

(E) other additives

The polyarylene sulfide resin composition according to an embodiment of the present invention is a coupling agent, antioxidant, lubricant, colorant, light stabilizer, UV stabilizer, plasticizer, foaming agent, rust inhibitor, or It may further include one or more various additives such as flame retardants.

As an example, the coupling agent improves the dispersion and wettability of the filler, and as a result, serves to improve the flashing properties along with mechanical properties such as strength and toughness of the resin composition, specifically, a silane-based compound May be, and more specifically, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl) ethyltrimethoxysilane containing epoxy groups such as Silane compounds; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanato Isocyanate group-containing silane compounds such as propylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane; amino group-containing silane compounds such as γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane; and silane compounds containing a hydroxy group such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane, and any one or a mixture of two or more of them may be used.

The coupling agent may be used after preliminary treatment, specifically, surface treatment, for the filler in advance, or may be used alone as an additive.

If 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, so when considering moldability as well as mechanical properties and flashing properties due to the inclusion of the coupling agent, 100 weight of the polyarylene sulfide resin It may be included in an amount of 0.1 to 10 parts by weight based on parts.

In addition, the antioxidant exhibits an antioxidant effect such as improving thermal stability of the resin composition, and a phosphorus-based, phenol-based, amine-based, or sulfur-based antioxidant may be used. For example, the phosphorus antioxidant may include a phosphate ester such as (Triphenylphosphate; TPP), (Triethyl Phosphate; TEP); Diethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, bis(2,6-dit -Butyl-4-methylphenyl) pentaerythritol diphosphite (Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate), bis (2,4-dit-butylphenyl) pentaerythritol diphosphite (bis (2,4-di-tert-butylphenyl)pentaerytryltol diphosphate), bis(2,4-dicumylphenyl) pentaerythritol diphosphite (bis(2,4-dicumylphenyl)pentaerythritol-diphosphite), or distearyl pentaerythritol depot Phosphonates such as distearyl penta erythritol diphosphate; Phosphinate; Phosphine oxide; Phosphazene; Or a metal salt thereof, and any one or a mixture of two or more of them may be used.

Moreover, as said phenolic antioxidant, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, thiodiethylene bis[3-(3,5) -Di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) Propionamide] and other hindered phenol compounds, and any one or a mixture of two or more of them may be used.

When the antioxidant is included in an excessive amount, it may be gasified during melt-kneading or injection molding, thereby causing deterioration of the working environment, and thus 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.

In addition, the lubricant increases moldability, prevents friction between the polyarylene sulfide resin composition and the metal of the mold, and serves to provide releasability during desorption in the mold. Specifically, olefin-based wax, Montan-based Wax, montanic acid ester wax, and the like may be used.

When the lubricant is included in an excessive amount, there is a risk of deterioration in moldability, and thus the amount of the lubricant may be 0.1 to 5 parts by weight based on 100 parts by weight of the polyarylene sulfide resin.

In addition, as the colorant, various conventional organic or inorganic pigments known in the art may be used. Specifically, titanium dioxide (TiO ₂ ), carbon black, etc. may be mentioned, and among these, carbon black may be used. The colorant may be included 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 in consideration of haze characteristics and mechanical properties of the polyarylene sulfide resin composition.

In addition, the polyarylene sulfide resin composition may be polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyether depending on the application. Synthetic resins such as ketone, polyarylene, polyethylene, polypropylene, polytetrafluoroethylene, polydifluoroethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenolic resin, urethane resin, liquid crystal polymer, or polyolefin rubber, It may further contain elastomers such as fluorine rubber and silicone rubber.

As described above, the polyarylene sulfide resin composition according to an embodiment of the present invention includes 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 the filler, and optionally may further include 0.1 to 10% by weight of one or more other additives, wherein the filler includes a fibrous filler and a granular filler in a weight ratio of 1.5:1 to 2.5:1, More specifically, by including it in a weight ratio of 2.25:1 to 2.5:1, outgassing and variability are suppressed while maintaining excellent mechanical properties, thereby exhibiting excellent adhesive properties.

More specifically, the polyarylene sulfide resin composition is 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 the filler, and optionally may further include 0.1 to 10% by weight of one or more other additives, wherein the filler includes a fibrous filler and a granular filler in a weight ratio of 1.5:1 to 2.5:1, More specifically, by including in a weight ratio of 2.25:1 to 2.5:1, the above effects can be further improved by optimizing the content of the components.

After mixing the polyarylene sulfide resin composition according to the embodiment of the present invention having the above composition, a polyarylene sulfide resin, a polyarylene ether resin, a fibrous filler and a granular filler, and optionally other additives, It can be produced by melt-kneading.

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

In addition, the melt-kneading process may be performed using a single-screw or twin-screw extruder, a Banbury mixer, a mixing roll, or a kneader, and more specifically, a shear force is provided to improve the dispersibility of various additives during melt-kneading. Can be carried out using a twin screw extruder.

The polyarylene sulfide resin composition according to an embodiment of the present invention as described above includes a fibrous filler and a granular filler together with a polyarylene ether resin, and further, the content of constituents including them is optimized As a result, the occurrence of bari is suppressed, and excellent mechanical properties and metal bonding properties can be exhibited.

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

In addition, the resin composition may have a tensile strength of 150 Mpa or more, more specifically 150 to 180 Mpa, measured at a rate of 5 mm/min according to ASTM D638.

In addition, the resin composition has a flexural strength of 230 Mpa measured at a rate of 5 mm/min according to ASTM D790. It may be above, more specifically 230 to 250 Mpa.

In addition, the resin composition may have a metal adhesive strength of 190 Mpa or more, more specifically 190 to 220 MPa.

In addition, the resin composition may have a spiral test (barrel temperature of 310° C.) of 0.06 g or less.

In addition, the resin composition may have an outgas generation amount of 200 cc or less, more specifically 150 cc or less.

As described above, the polyarylene sulfide resin composition according to an embodiment of the present invention has excellent mechanical properties, and thus various molded parts, specifically undrawn, 1 by injection molding, injection compression molding, brow molding or extrusion molding. It can be molded into various forms such as various films, sheets, fibers, or pipes, such as axial stretching and biaxial stretching, and may be more suitable for injection molding applications because it has excellent releasability.

Accordingly, according to another embodiment of the present invention, a molded article manufactured by using the polyarylene sulfide resin composition is provided.

The molded product can be widely used in various fields such as automobiles, electric/electronic products, or mechanical parts. In particular, as it has excellent mechanical properties, outgassing and barri are suppressed, and has excellent metal bonding properties, computer parts Alternatively, it may be useful for manufacturing molded products that require high precision or thin thickness, such as connectors.

Hereinafter, the action and effect of the invention will be described in more detail through specific examples of the invention. However, this is presented as an example of the invention, and the scope of the invention is not limited to any meaning.

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° C./5 kg according to ASTM D1238) and a Tm of 280° C. was used.

(A2) polyphenylene sulfide (PPS)

A crosslinked polyphenylene sulfide resin having a melt index of 500 to 1000 g/min (measured at 315 °C/5 kg according to ASTM D1238) and a Tm of 280 °C was used.

(B) polyarylene ether

A poly(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

Fiber diameter 10 ~ 13㎛, chop (chop) length 3 ~ 4mm, glass fiber surface-treated with epoxy silane was used.

(C2) Granular filler

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

(D) aluminosilicate

Calcium alumino silicate having a number average particle diameter of 2.5 μm and a bulk density of 0.43 g/ml was used.

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

After mixing each of the components in the composition shown in the table below, using a twin screw extruder having a screw L/D of 42 and a Φ value of 40 mm, melting and kneading at 300 to 330 °C to prepare a resin composition in a pellet form I did.

After drying the prepared resin composition in the form of pellets at 120° C. for 3 hours or more, an ASTM standard specimen was injected and manufactured at an injection temperature of 320° C. and a mold temperature of 120° C., and 48 hours in an environment with a temperature of 23° C. and a relative humidity of about 60%. Left unattended.

Ingredients 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 - - - - - - Polyarylene ether (B) - - - 3 3 3 5 7 3 3 Fibrous filler
(C1) 35 35 45 30 30 45 45 45 45 45 Granular filler (C2) 30 30 20 35 35 20 20 20 20 20 Aluminosilicate (D) - - - - - - - - One 2

In Table 1, the content unit of each component is weight%

[Test Example]

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

Tensile strength: It was measured according to standard measurement ASTM D638 using a specimen, and at this time, the cross head speed of the tensile tester was measured as 5 mm/min.

Flexural strength: It was measured according to ASTM D790, and at this time, the crosshead speed of the tensile tester was measured as 1.3mm/min.

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

Barrier generation amount: After cutting a thin portion sandwiched between a gas vent mold of different size at the end of a 12.7×127×3mm bar specimen, the weight of the cut thin portion was measured.

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

Adhesive properties: After fixing a zinc plate with a size of 0.8 x 0.8 cm on the specimen, a modified acrylic adhesive was evenly applied to adhere to the specimen. The bonded specimen was measured for adhesion by the maximum force until fracture of the zinc plate adhered to the specimen using a bending tester.

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 Bari generation amount
(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 Amount of outgas
(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 to which calcium aluminosilicate was added, the amount of outgassed was significantly reduced in light of Comparative Examples 1 to 8, and as a result, metal adhesion was greatly increased.

In addition, by including the fibrous filler and the granular filler mixed at an optimum mixing ratio together with the polyarylene ether resin, the amount of bari generated while maintaining excellent mechanical properties was greatly reduced.

From these results, the polyarylene sulfide resin composition according to the present invention maintains excellent mechanical properties while suppressing outgassing and variability, thereby exhibiting improved metal adhesion properties. It can be seen that it can be useful for the manufacture of molded articles for metal replacement, especially molded articles requiring high precision or 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;
1 to 3% by weight of aluminosilicate; And
Including 60 to 75% by weight of the filler,
The filler comprises a fibrous filler and a granular filler in a weight ratio of 1.5:1 to 2.5:1, polyarylene sulfide resin composition.
The method of claim 1,
The polyarylene sulfide resin is 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, a polyarylene sulfide resin composition.
The method of claim 1,
The polyarylene sulfide resin is a polyarylene sulfide resin composition of a linear polymer resin.
The method of claim 1,
The polyarylene ether resin 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 , a polyarylene sulfide resin composition.
The method of claim 1,
The polyarylene ether resin is 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 and a copolymer thereof, including any one or two or more selected from the group consisting of, polyarylene sulfide resin composition.
The method of claim 1,
The fibrous filler is a glass fiber having an aspect ratio of more than 1, a polyarylene sulfide resin composition.
The method of claim 6,
The glass fiber has a fiber diameter of 10 to 15 μm and a chop length of 1 to 10 mm, a polyarylene sulfide resin composition.
The method of claim 1,
The granular filler has an average particle diameter (D ₅₀ ) of 3 to 10 μm, a polyarylene sulfide resin composition.
The method of claim 1,
The granular filler is calcium carbonate, polyarylene sulfide resin composition.
The method of claim 1,
At least one of the fibrous filler and granular filler is surface-treated with a compound selected from the group consisting of epoxy resins, acrylic resins, urethane resins, coupling agents, lubricants, fatty acids, fatty acid esters, resin acids, and higher alcohol added isocyanate compounds. The polyarylene sulfide resin composition.
The method of claim 1,
The alumino silicate has a number average particle diameter of 1 to 30 μm, and a bulk density of 0.30 to 0.60 g/ml, a polyarylene sulfide resin composition.
The method of claim 1,
The alumino silicate is calcium aluminosilicate, a polyarylene sulfide resin composition.
The method of claim 1,
A coupling agent, an antioxidant, a lubricant, a pigment, a light stabilizer, a UV stabilizer, a plasticizer, a foaming agent, a rust inhibitor, and further comprising any one or two or more additives selected from the group consisting of a flame retardant, polyarylene sulfide resin composition.
A molded article manufactured from the polyarylene sulfide resin composition according to claim 1.