TWI731857B - Polyarylene sulfide composition having improved adhesion to metals - Google Patents

Abstract

The present invention provides a resin composition comprising a polyarylene sulfide; and a polyvinyl acetal resin, with a small amount of outgassing, and the polyarylene sulfide resin composition according to the present invention has excellent heat deflection temperature and adhesive strength to metals, with a small amount of outgassing; therefore, it may be used for manufacturing products requiring precise molding.

Description

Polyarylene sulfide composition with improved adhesion to metal (1) Field of invention

The present invention relates to a polyarylene sulfide composition, which has improved impact strength and adhesion to metals, accompanied by a small amount of exhaust gas and a high heat distortion temperature.

Background of the invention

At present, the demand for representative engineering plastic polyarylene sulfide (PAS) has increased. It is used in various electronic goods and products used in high temperature and corrosive environments, due to its high heat resistance, Chemical resistance, flame retardancy and electrical insulation.

Polyphenylene sulfide (PPS) is the only polyarylene sulfide on the market. PPS is widely used in the housing or main parts of automobile equipment and electrical or electronic devices due to its excellent mechanical, electrical and thermal properties and chemical resistance.

The main process for the commercial production of PPS is the solution polymerization of p-dichlorobenzene (pDCB) and sodium sulfide in a polar organic solvent such as N-methylpyrrolidone, which is called the Macallum process.

When polyarylene sulfide is produced by the McGregor process, however, solution polymerization using sodium sulfide, etc. may result in the salt form By-products (for example, sodium chloride). Since such by-products in the salt form and any residual organic solvents impair the performance of the electronic device, they must be removed. Therefore, additional washing or drying processes are required. Furthermore, the polyarylene sulfide produced by the McDonald's process has a powder form, which may make the subsequent process inconvenient and impair its operability (see US Patent Nos. 2,513,188 and 2,583,941).

In order to solve the above problems, a process for producing polyarylene sulfide such as PPS by melt polymerization of a reactant containing a diiodo aromatic compound and elemental sulfur has been proposed. Because this process produces neither by-products in the salt form nor the use of organic solvents in the manufacture of polyarylene sulfide, it does not require any separate process for removing such by-products or organic solvents. Furthermore, the finally obtained polyarylene sulfide has a pellet form, which may facilitate the subsequent manufacturing process and improve its operability.

On the other hand, conventional PPS has a problem of poor adhesion to metal. Because a large amount of exhaust gas (ie, low molecular weight oligomers) is generated on the flow front during injection molding, when the PPS adheres to the metal , Which prevents the micropores on the metal surface from being filled. As an alternative for improving the adhesion of PPS to metals, a resin composition prepared by compounding PPS with a polyolefin containing a polar group and a compatibilizer has been proposed. However, it has been found that the use of such alloys or oligomers degrades the mechanical properties of PPS and weakens the thermal properties of PPS.

Correspondingly, the development has excellent adhesion properties to metals, along with a reduced amount of exhaust in the flow head, which is a potential problem in conventional metal-adhesive plastics, and a reduced amount of by-products such as chloride A PAS composition system of the material is required.

Summary of the invention

One object of the present invention is to provide a polyarylene sulfide composition which has excellent adhesion properties to metals and accompanied by a small amount of exhaust gas from the flow head.

A resin composition of the present invention, which comprises: (a) a polyarylene sulfide; and (b) a polyvinyl acetal resin, which contains 45 to 95 mol% of the repeating unit of formula 1, 0 to 10 mol% The repeating unit of formula 2 and 5 to 50 mol% of the repeating unit of formula 3, wherein the amount of exhaust gas is 300 ppm or less:

其中R為異丙基或甲基。 [Equation 3]

Where R is isopropyl or methyl.

The resin composition according to the present invention has excellent adhesion properties to metals without compromising the unique excellent mechanical and thermal properties of PPS, accompanied by a small amount of exhaust gas. Therefore, it can be used in a variety of applications, including electronic components and automotive components integrally formed by injection insert molding. Further, the resin composition of the present invention may be useful as a material for internal components used in such electronic devices, such as mobile phones, notebook computers, etc., because of its small amount, it may weaken them in other ways. A by-product of the performance of electronic devices in the salt form.

Fig. 1 is a partial schematic diagram showing the process of preparing a sample for testing the adhesion strength to metal using the resin composition of the present invention.

Detailed description of the preferred embodiment The best mode for carrying out the invention

The resin composition of the present invention includes: a polyarylene sulfide; and a polyvinyl acetal resin containing 45 to 95 mol% of the repeating unit of formula 1, 0 to 10 mol% of the repeating unit of formula 2, and 5 to 50mol% of the repeating unit of formula 3, where the amount of exhaust gas is 300ppm or less:

其中R為異丙基或甲基。

Where R is isopropyl or methyl.

In the resin composition according to the present invention, the amount of exhaust gas is 300 ppm or less, specifically 150 to 300 ppm.

In the resin composition according to the present invention, the amount of chloride is 300 ppm or less, 200 ppm or less, or 100 ppm or less, specifically 0 to 100 ppm, more specifically 70 ppm or less.

In the following, the components of the composition are described in detail.

The resin composition of the present invention contains a polyarylene sulfide.

The polyarylene sulfide may be contained in an amount of 20 to 85% by weight, preferably 30 to 80% by weight, based on the total amount of the composition. When the amount of the polyarylene sulfide is 20% by weight or more, mechanical strength such as impact strength does not decrease. Further, when the amount When it is 85% by weight or less, the adhesion effect to metal becomes excellent.

The polyarylene sulfide comprises an arylene sulfide repeating unit and an arylene disulfide repeating unit, and the weight ratio of the arylene sulfide repeating unit to the arylene disulfide repeating unit ranges from 1. : 0.0001 to 1:0.5.

The arylene sulfide repeating unit may be contained in an amount of 95% to 99.99% by weight, based on the total weight of the polyarylene sulfide, and the arylene disulfide repeating unit may Included in an amount of 0.01 to 5% by weight, based on the total weight of the polyarylene sulfide.

The polyarylene sulfide may have a number average molecular weight of 3,000 to 1,000,000, and a polydispersity of 2.0 to 4.0. Polydispersity is defined as the ratio of weight average molecular weight to number average molecular weight, which indicates a relative Narrow dispersion.

The polyarylene sulfide may have a melting point ranging from 270 to 290°C, specifically from 275 to 285°C, more specifically about 280°C. Further, when measured by a rotating disk-type viscometer at a temperature of melting point + 20°C, the melt viscosity may range from 100 to 5,000 poises, specifically from 500 to 3,000 poises , More specifically about 2,000 poise.

Since the polyarylene sulfide used in the present invention contains a certain amount of arylene disulfide repeating units, it is better than a polyarylene sulfide having the same molecular weight but composed of only arylene sulfide repeating units. The base sulfide has a lower melting point, which lowers the process temperature and reduces the amount of exhaust gas generated as a by-product during the molding process. Further, the final production Polyarylene sulfide has excellent physical properties.

The polyarylene sulfide is not specifically limited as long as it satisfies the properties discussed above. For example, the polyarylene sulfide may be produced by solution polymerization. Further, the polyarylene sulfide meeting the above-discussed properties improves the adhesion of a resin composition to metal.

Specifically, the polyarylene sulfide may be produced by the method disclosed in Korean Patent Publication No. 2011-0102226, which may include steps, for example, (a) implementing a diiodo aromatic compound The polymerization reaction of the reactant of the compound and a sulfur compound; (b) during the polymerization reaction, 0.1 to 20 parts by weight of the sulfur compound is further added, and 100 parts by weight of the sulfur compound contained in the reactants is used as Benchmark.

In the above-mentioned method, since a small amount of sulfur compound is further added during the polymerization reaction, disulfide type bonds may be formed in the polymer. The disulfide bond and the polymer chain contained in the polyarylene sulfide continuously participate in the sulfur exchange reaction, an equilibrium reaction type, so that the polymer chain contained in the polyarylene sulfide is The molecular weight becomes uniform. In particular, the degree of polymerization of the reactants may be approximately uniform due to the equilibrium reaction of the sulfur exchange reaction; therefore, the formation of polyarylene sulfide polymer chains with too large or too small molecular weight may be inhibited.

The reactants containing a diiodo aromatic compound and a sulfur compound may be melt blended before the polymerization step. The diiodo aromatic compound may be used in an amount of 1,000 to 1,400 parts by weight based on 100 parts by weight of the sulfur compound supplied before polymerization.

In step (a), 1 to 20 parts by weight of the polymerization terminator may be added based on 100 parts by weight of the sulfur compound supplied to the reactants. The polymerization terminator is not specifically limited, as long as it can terminate the polymerization by removing the iodine group contained in the polymer to be prepared. As the polymerization terminator, it is possible to use at least one selected from the group consisting of diphenyl sulfide, diphenyl ether, biphenyl (or diphenyl), benzophenone, dibenzothiazole Dibenzothiazyl disulfide, monoiodoaryl compound, benzothiazole, benzothiazole sulfenamide, thiuram, dithioamine Alkyl formate and diphenyldisulfide (diphenyldisulfide).

The diiodo aromatic compound, which may be used in the polymerization reaction of polyarylene sulfide, is selected from at least one of the following group consisting of, but not limited to: diiodobenzene (DIB) , Diiodonaphthalene, diiodobiphenyl, diiodobiphenol and diiodobenzophenone (diiodobenzophenone).

The conditions of step (a) are not specifically limited, as long as the reaction of the diiodo aromatic compound and the sulfur compound can be initiated. Specifically, the polymerization may be performed under reaction conditions of increasing temperature and decreasing pressure. Specifically, the temperature is increased and the pressure is decreased, from the initial reaction conditions of a temperature of 180 to 250°C and a pressure of 50 to 450 torr, to a final reaction condition of a temperature of 270 to 350°C and a pressure of 0.001 to 20 torr . The reaction may be performed for 1 to 30 hours.

The polyarylene sulfide used in the present invention contains few by-products in the salt form, unlike those produced by conventional solution polymerization methods. The polyarylene sulfide. The resin composition of the present invention may contain a chloride amount of 300 ppm or less, 200 ppm or less, or 100 ppm or less, specifically 0 to 100 ppm, more specifically 60 ppm or less.

On the other hand, the resin composition of the present invention includes a polyvinyl acetal resin.

Since the above-mentioned resin composition contains a polyvinyl acetal resin, compared with the conventional PPS resin composition, it enhances the adhesion strength to metal.

The polyvinyl acetal resin may have a number average molecular weight of one of 20,000 to 300,000, specifically 30,000 to 250,000.

The polyvinyl acetal resin may include repeating units selected from the group consisting of formulas 1 to 3. For example, it may be produced by the copolymerization of the polyvinyl acetal repeating unit of formula 1, the polyvinyl acetate repeating unit of formula 2, and the polyvinyl alcohol repeating unit of formula 3:

其中R為異丙基或甲基。

Where R is isopropyl or methyl.

Specifically, the repeating unit of formula 1 may be included in one of 45 to 95 mol%, 50 to 95 mol%, 55 to 85 mol%, or 50 to 85 mol%, and the total number of the polyvinyl acetal resin is Benchmark. The greater the number of repeating units of Formula 1, the better. The number of repeating units of the above formula 1 may improve its compatibility with the resin and reduce the rate of water absorption.

The repeating unit of formula 2 may be included in one of 0 to 10 mol%, 0 to 6 mol%, 0 to 5 mol%, or 1 to 5 mol%, based on the total amount of the polyvinyl acetal resin. The number of repeating units of the above formula 2 may increase the glass transition temperature of the resin composition and reduce its viscosity.

The repeating unit of formula 3 may be included in one of 5 to 50 mol%, 15 to 45 mol%, or 10 to 40 mol%, based on the total amount of the polyvinyl acetal resin. The number of repeating units of the above formula 3 may increase the adhesion of the resin composition to metal and improve its compatibility with the resin.

The polyvinyl acetal resin may be contained in an amount of 0.5 to 15%, 1 to 8%, or 5 to 8% by weight, based on the total amount of the composition. When the amount of the polyvinyl acetal resin is 0.5% by weight or more, the adhesion strength to metal becomes excellent. Further, when the quantity is At 15% by weight or less, the mechanical strength is not impaired.

The polyvinyl acetal resin may have a glass transition temperature of 50 to 120°C, 60 to 110°C, or 60 to 70°C, and have a content of less than 5% by weight of volatile substances.

Further, the polyvinyl acetal resin may use a polyvinyl acetal resin having a functional group such as a carboxyl group in order to enhance the compatibility with PAS and the adhesion strength to metal.

The resin composition of the present invention may further include a component selected from the group consisting of elastomers, fillers, shock absorbers, adhesion enhancers, stabilizers, pigments, and combinations thereof.

The elastomer is selected from polyvinyl chloride elastomers, polyolefin elastomers, polyurethane elastomers, polyester elastomers, polyamide elastomers, polybutadiene elastomers, and glycidyl methacrylate It is possible to use a thermoplastic elastomer of this group composed of a terpolymer of methyl acryl ester (methyl acryl ester) and a combination thereof. A preferred elastomer is a terpolymer of glycidyl methacrylate and methyl acrylate.

The elastomer may be contained in an amount of 1 to 15% by weight, preferably 3% to 10% by weight, based on the total amount of the resin composition. The addition of elastomer to the resin composition of the present invention may impart toughness to PAS, which prevents the interface separation between the resin and the metal that may be caused by temperature changes after being adhered to the metal under other conditions.

As the filler, at least one organic or inorganic filler selected from the group consisting of glass fiber, carbon fiber, boron fiber, glass beads, glass flakes, talc and calcium carbonate may be used. A better filler For glass fiber. The filler may be in powder or flake form, but is not limited thereto.

The glass fiber used as a filler may be selected from the group consisting of glass fiber treated with siloxane oxide, glass fiber treated with aminosilane, and combinations thereof. Specifically, the glass fiber may be a glass fiber treated with siloxane oxide.

The filler may be included in an amount of 5 to 50% by weight, specifically 10 to 40% by weight, based on the total amount of the resin composition.

As the pigment, conventional organic or inorganic pigments known in the art, for example, an organic or inorganic pigment selected from _{the group consisting of titanium dioxide (TiO 2} ), carbon black, and combinations thereof may be used. Preferably, titanium dioxide may be used.

The pigment may be included in an amount of 0.1 to 10% by weight, preferably 0.3% to 7% by weight, based on the total amount of the composition.

The shock absorber, adhesion enhancer, and stabilizer may be regular users in the art.

The stabilizer may be an antioxidant, light stabilizer, UV stabilizer, and combinations thereof.

The antioxidant helps maintain the high heat resistance and thermal stability of the resin composition according to the present invention. An example of an antioxidant may be a phenolic antioxidant, an amine antioxidant, a sulfur antioxidant, or a phosphorus antioxidant.

As phenolic antioxidants, hindered phenol compounds are preferably used Things. Specific examples are tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, thiodiethylenebis[3-(3,5-di Tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionate) Amine], and so on.

Examples of phosphorus antioxidants are tris(2,4-di-tert-butylphenyl)phosphate, O,O'-octadecylpentaerythritol bis( Phosphite) (O,O'-dioctadecylpentaerythritolbis(phosphite)), bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, 3,9-bis(2,4-di-tert-butylbenzene) Oxy)-2,4,8,10-tetraoxa-3,9-diphosphospiro[5.5]undecane (3,9-bis(2,4-di-tert-butylphenoxy)-2,4, 8,10-tetraoxa-3,9-diphospaspiro[5.5]undecane), and so on.

In addition to the above components, the resin composition of the present invention may further include various conventional additives known in the art, such as plasticizers, nucleating agents, and the like.

Further, the resin composition according to the present invention may contain various lubricants for enhancing molding. In particular, hydrocarbon lubricants may be used to prevent friction between the resin and the mold metal, and to grant mold release from the mold... etc.

The resin composition of the present invention may have a heat distortion temperature of 220 to 260°C, as measured according to ISO 75.

The resin composition of the present invention may have an adhesion strength to metal of 50 MPa or higher, 50 to 90 MPa, or 70 to 90 MPa, as measured in accordance with ASTM D 3163 on a metal adhesion test sample, which is obtained by From insert injection to etched in a certain pattern Obtained on aluminum plate.

The resin composition of the present invention may have an impact strength of 6.5KJ/m ² or higher, 7KJ/m ² or higher, 7 to 9KJ/m ² , or 7.5 to 9KJ/m ² , as measured according to ISO 179 .

Since the resin composition of the present invention includes the polyarylene sulfide and polyvinyl acetal resin discussed above, it may have excellent adhesion properties to metals without compromising the unique excellent mechanical and thermal properties of PAS. A small amount of exhaust.

In another aspect, the present invention provides a molded article made from the resin composition.

The resin composition of the present invention may be used according to methods known in the art, such as biaxial extrusion, to manufacture molded products, which have excellent adhesion to metals and may be used in various applications.

These molded articles may be in various forms, including films, sheets, or fibers according to the present invention. These molded products may be injection molded products, extrusion molded products, or blow molded products. In the case of injection molding, the temperature of the mold may be about 130°C or higher in view of crystallization.

If the molded articles are in the form of films or sheets, they may be manufactured in various films or sheets, such as non-oriented, uniaxially oriented, or biaxially oriented films or sheets. These molded products may be used as non-oriented fibers, stretched fibers, or super stretched fibers... etc., and may also be used as fabrics, knitted fabrics, non-woven fabrics (spunbonded, melt blown (meltblow), or man-made fibers) (staple)), rope or net.

The above-mentioned molded products may be used as electrical/electronic parts, construction Coating of materials, auto parts, mechanical parts, or basic commodities, areas in contact with chemicals, or chemical-resistant industrial fibers.

Invention Mode

In the following, the present invention is explained in detail by examples. The following examples are intended to further illustrate the present invention without limiting its scope.

Preparation Example 1: Preparation of PPS

As a catalyst, 40 kg of p-diiodobenzene, 3.4 g of sulfur, and 150 g of 1,3-diiodo-4-nitrobenzene were melt blended in a reactor at 180°C. The mixed reactants undergo a polymerization reaction, and the temperature is increased from 180°C to 340°C, and the pressure is reduced from 350 torr to 10 torr. At 5 hours after the start of polymerization, 150 g of sulfur and 100 g of diphenyl sulfide as a polymerization terminator were added to the reaction mixture, and the polymerization reaction was performed for an additional 3 hours to obtain a polymer .

The melt viscosity (MV), melting point (Tm), and weight ratio of repeating units of the obtained PPS polymer were measured according to the following method. As a result, the PPS polymer has an MV of 2,000 poise, a Tm of 280°C, a number average molecular weight of 16,400, and a weight ratio of arylene sulfide unit to arylene disulfide unit of 1:0.003.

Melt viscosity

The melt viscosity is measured by a rotating disc viscometer at Tm+20°C. In the frequency sweep method, the angular frequency is measured from 0.6 to 500 rad/s, and the viscosity at 1.0 rad/s is defined as the melt viscosity.

Melting point

Using a differential scanning calorimeter (DSC), the melting point is when the temperature rises from 30 to 320°C at a rate of 10°C/min, cools to 30°C, and then changes from 30 to 320°C at a rate of 10°C/min. 30 is raised to 320°C and measured.

Gravimetric analysis of repeating units

2 mg of the produced PPS polymer was burned at 1,000°C in an Automatic Quick Furnace. The sulfur system is trapped in an absorption solution (for example, hydrogen peroxide) and ionized. The sulfide ions are separated in an ion chromatography column, and their quantity is _{measured by a standard substance for sulfur (K 2} SO ₄ ). The difference between the measured amount of sulfur and the theoretical amount of sulfur is calculated as the amount of arylene disulfide.

Example 1: Preparation of PPS resin composition

67% by weight of the PPS resin obtained in Preparation Example 1, 15% by weight of siloxane-treated glass fiber (OCV-910, Owens Corning), 8% by weight of elastomer ( Lotader AX-8900, Arkema), 5% by weight of polyvinyl acetal resin (BM-S, Sekisu), and 5% by weight of TiO ₂ white pigment (label 2233, Crowe Kronoss is fed to a twin-screw extruder to prepare a resin composition.

The polyvinyl acetal resin is made by copolymerizing 70 to 76 mol% by weight of polyvinyl butyral repeating units, 2 to 8 mol% by weight of polyvinyl acetate repeating units, and about 22 mol% by weight of polyvinyl alcohol repeating units. Unit and prepared. Furthermore, the polyvinyl acetal resin has one of 53,000 Mesh average molecular weight, 3% by weight content of volatile substances, and 60°C glass transition temperature.

The extruder has a diameter of 40mm and an L/D (SM Platek) of 44. The extrusion conditions are a screw speed of 250 rpm, a feed rate of 60 kg/hour, a barrel temperature of 280 to 300° C., and a torque of 60%. The above-mentioned materials are fed through a total of three feeders. Among them, the first feeder is used to feed the PPS resin, elastomer, and polyvinyl acetal resin; the second feeder feeds the white Pigment; and a third feeder feeds the glass fiber.

Examples 2 to 6

The same procedure as in Example 1 was repeated to prepare the PPS resin composition, except for the components and their quantities as described in Table 2 below.

Comparative example 1

The same procedure as in Example 1 was repeated to prepare a PPS resin composition, except that BPA type epoxy resin (YD-017, Guodu Chemical Co., Ltd.) was used instead of the polyvinyl acetal resin.

Comparative example 2

The same procedure as in Example 1 was repeated to prepare a PPS resin composition, except for the components and their quantities as described in Table 2 below.

Comparative example 3

The same procedure as in Example 1 is repeated to prepare a PPS resin composition, except that the components and their quantities are described in Table 2 below As mentioned above, and no polyvinyl acetal resin is used.

Comparative example 4

The same procedure as in Example 1 was repeated to prepare a PPS resin composition, except that PPS 1 (0205P4, Ticona, a linear PPS) prepared by the solution polymerization method was substituted for the one obtained in Preparation Example 1. Those who use outside.

Comparative example 5

The same procedure as in Example 1 was repeated to prepare a PPS resin composition, except for the components and their quantities as described in Table 2 below, PPS 1 (0205P4, Ticona) prepared by the solution polymerization method , A linear PPS) is used instead of the one obtained in Preparation Example 1, and no polyvinyl acetal resin is used.

Comparative example 6

The same procedure as in Example 1 was repeated to prepare a PPS resin composition, except that PPS 2 (P6, Chevron Philips, a cross-type PPS) prepared by the solution polymerization method was replaced in the preparation In addition to the use of those obtained in Example 1.

Table 1 below shows the manufacturers of the components used in Examples 1 to 6 and Comparative Examples 1 to 6.

Test case

The physical properties of the PPS resin compositions prepared in the Examples and Comparative Examples were tested as described below. These results are shown in Table 2.

First, the PPS resin compositions prepared in the Examples and Comparative Examples were injected at 310° C. to prepare injection molded samples.

(1) Exhaust quantity

Place 2 g of the injection molded sample in a 20 mL sealed vial. After heating the vial in a head space device at 260°C for 30 minutes, the generated gas system is automatically delivered to a gas chromatography mass spectrometer. Then, each component is separated by a capillary column for qualitative analysis, and the quantity of each component in the sample is quantitatively analyzed using benzothiazole as a standard substance.

(2) Heat distortion temperature (HDT)

The thermal deformation temperature of the injection molded sample is measured according to ISO 75.

(3) Impact strength (notch)

According to the ISO 179 method, the impact strength of an injection molding test specimen (80mm (length) × 10mm (width) × 4mm (thickness)) is obtained by V-notch summer Ratio method (V-notch Charpy method) measurement.

(4) Adhesion strength to metal

A specific etched aluminum sample (length: 70mm, width: 18mm and height: 2mm) is placed between a fixed mold and a movable mold in a two-plate injection molding machine. Each of the PPS resin compositions prepared in the examples and comparative examples is inserted between the two-plate molds, and the injection speed is 50 mm/s, an injection pressure of 120 MPa, and a mold temperature of 150° C. Ton Engel (Engel) injection molding machine. The molded parts were taken out of the mold to prepare test specimens (length: 70mm, width: 10mm and height: 3mm) for measuring the adhesion strength to metal (see Figure 1). The adhesion strength of these test specimens to metal is measured in accordance with ASTM D 3163.

(5) Chloride content

The resin used as the internal component material of electronic devices such as mobile phones, notebook computers, etc., should have a low chloride by-product level to prevent the performance of these electronic devices from being impaired. Accordingly, for the PPS resin prepared in Preparation Example 1, and the PPS1 and PPS2 resins prepared by the solution polymerization method, the chloride content was measured as follows.

First, a 50 mg resin sample is heated at about 1,000°C to incinerate any organic substances, trapped in a halogen or sulfur absorbing solution, and then analyzed by ion chromatography (Ion Chromatography, Auto Quick Furnace).

As a result, the chlorination of the PPS resin prepared in Preparation Example 1 The content is 0 ppm, and those PPS1 and PPS2 resins prepared by the solution polymerization method are 1,300 ppm and 2,300 ppm, respectively. These results show that the PPS resin prepared in Preparation Example 1 has a very low amount of impurities.

For the resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 6, the chloride content was measured according to the same procedure as above. These results are shown in Table 2.

As shown in Table 2, the resin compositions according to the present invention Compared with those of Comparative Examples 4 to 6 containing PPS1 or PPS2 produced by solution polymerization, the amount of exhaust gas is reduced by 6.5 times.

Further, Examples 1 to 6 containing polyvinyl acetal resin have an adhesive strength of 75 to 86 MPa to metals, which is a great improvement for Comparative Example 1 containing BPA epoxy resin (ie, 29 MPa). Furthermore, the composition of Comparative Example 2 containing excessive polyvinyl acetal resin has reduced HDT and impact strength, while the composition of Comparative Example 3 that does not contain polyvinyl acetal resin has greatly reduced adhesive strength to metals.

On the other hand, the resin composition of the present invention has an ^{impact strength of 7.5 to 9.0 KJ/m 2} and thus exhibits superior performance to those prepared in Comparative Examples 1 to 3, which contains epoxy resin but does not contain Polyvinyl acetal resin, or excessive polyvinyl acetal resin.

Further, the resin compositions of Examples 1 to 6 have a chloride content of 0 ppm, while those of Comparative Examples 4 and 5 containing PPS 1 prepared by solution polymerization have a chloride content of 860 to 938 ppm, and contain Comparative Example 6 of PPS 2 prepared by solution polymerization has a chloride content of 1482 ppm, which indicates a large difference in the amount of impurities.

It also noticed that the resin compositions of the examples have a low chloride content, compared with Comparative Example 1 containing epoxy resin instead of polyvinyl acetal resin, although it is contained in Preparation Example 1. PPS prepared in.

Therefore, the resin composition according to the present invention may have excellent adhesion to metal, impact strength and heat distortion temperature, accompanied by a reduced amount of exhaust gas. Therefore, it may be used in various fields, including hand Machines, electronic parts, automobile parts, etc., are integrally formed by injection and insert molding. Further, the resin composition according to the present invention may promote the superior performance of electronic devices because the resin composition does not contain impurities.

Claims (13)

A resin composition comprising: (a) a polyarylene sulfide; and (b) a polyvinyl acetal resin comprising 45 to 95 mol% of the repeating unit of Formula 1 and 0 to 10 mol% of the repeating of Formula 2 Unit, and 5 to 50 mol% of the repeating unit of formula 3, wherein the polyvinyl acetal resin is included in an amount in the range of 0.5 to 15 wt% based on the total amount of the composition; and the amount of exhaust gas is 300ppm or less:

Wherein R is isopropyl or methyl. Such as the composition of claim 1, further including one selected from the following The components of the group: elastomers, fillers, shock absorbers, adhesion enhancers, stabilizers, pigments, and combinations thereof. Such as the composition of claim 2, wherein the elastic system is a thermoplastic elastomer selected from the group consisting of polyvinyl chloride elastomers, polyolefin elastomers, polyurethane elastomers, polyester elastomers, and poly A group consisting of amide elastomers, polybutadiene elastomers, glycidyl methacrylate and methyl acryl ester terpolymers, and combinations thereof. The composition of claim 2, wherein the filler is at least one organic or inorganic filler selected from the group consisting of glass fiber, carbon fiber, boron fiber, glass beads, glass flakes, talc, and calcium carbonate . Such as the composition of claim 4, wherein the glass fiber is selected from the group consisting of epoxy silane treated glass fiber, amino silane treated glass fiber, and combinations thereof. Such as the composition of claim 2, wherein the pigment is an organic or inorganic pigment selected _{from the group consisting of titanium dioxide (TiO 2} ), carbon black, and combinations thereof. Such as the composition of claim 2, wherein based on the total amount of the composition, the pigment is included in an amount in the range of 0.1 to 10 wt%. Such as the composition of claim 1, wherein as measured according to ISO 75, the composition has a heat distortion temperature of 220 to 260°C. The composition of claim 1, wherein the composition has an adhesion strength to metal of 50 to 90 MPa as measured according to ASTM D 3163. Such as the composition of claim 1, wherein as measured according to ISO 179, the composition has an impact strength of ^{7 to 9 KJ/m 2.} The composition of claim 1, wherein the composition has a chloride content of 300 ppm or less. The composition of claim 11, wherein the composition has a chloride content of 100 ppm or less. The composition of claim 1, wherein the composition has a weight ratio of arylene sulfide repeating unit to arylene disulfide repeating unit ranging from 1:0.0001 to 1:0.5.

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