CN108603030B

CN108603030B - Polyarylene sulfide composition having excellent adhesion to metal

Info

Publication number: CN108603030B
Application number: CN201780008608.0A
Authority: CN
Inventors: 金亥里; 辛钟昱; 郑明旭; 安秉佑; 吴亨根
Original assignee: Sk化学公司
Current assignee: Hdc Polymerization Co ltd
Priority date: 2016-02-15
Filing date: 2017-01-18
Publication date: 2021-06-29
Anticipated expiration: 2037-01-18
Also published as: WO2017142217A1; KR20170095569A; TW201800486A; JP6707655B2; CN108603030A; JP2019504921A

Abstract

The present invention relates to a polyarylene sulfide composition having a small amount of outgas and excellent whiteness, acid resistance and metal adhesion. The polyarylene sulfide composition of the present invention exhibits a small amount of outgas and excellent whiteness, acid resistance and metal adhesion, and can be used as a resin composition for producing products requiring molding accuracy.

Description

Polyarylene sulfide composition having excellent adhesion to metal

Technical Field

The present invention relates to a polyarylene sulfide composition having a small amount of outgas and excellent whiteness, acid resistance and metal adhesion.

Background

Currently, polyarylene sulfide (hereinafter, referred to as "PAS") as a typical engineering plastic has an increasing demand for products and various electronic goods used in high-temperature and corrosive environments due to its high heat resistance, chemical resistance, flame retardancy, and electrical insulation. Polyphenylene sulfide (hereinafter referred to as "PPS") is the only commercially available polyarylene sulfide. PPS is widely used in housings or main parts of automobile equipment, electric or electronic devices because of its excellent mechanical, electrical, thermal and chemical resistance.

A method widely used for commercial production of PPS is solution polymerization of p-dichlorobenzene (hereinafter referred to as "pDCB") and sodium sulfide as raw materials in a polar organic solvent such as N-methylpyrrolidone, which is called a mcarone process (Macallum process). However, when PPS is produced by the macaron process, a solution polymerization process using sodium sulfide or the like may generate a byproduct (e.g., NaCl) in the form of a salt. Since the by-products in the form of salts may impair the performance of electronic parts, an additional washing or drying process or the like is required to remove the by-products and residual organic solvent (see U.S. Pat. nos. 2,513,188 and 2,583,941).

In order to solve the above problems, a method of preparing PAS such as PPS by melt polymerization of reactants containing diiodo aromatic compounds and elemental sulfur has been proposed. Since the method does not generate byproducts in the form of salts during the preparation of PAS and does not use an organic solvent, a separate process for removing the byproducts or the organic solvent is not required.

Meanwhile, the conventional PPS has a problem of poor adhesion to metals due to a large amount of outgas (i.e., low molecular weight oligomers) generated at the flow front of injection molding, which prevents micropores from being filled when the PPS adheres to metals, thereby reducing metal adhesion. As an alternative to improving the metal adhesion of PPS, a resin composition prepared by mixing PPS with a polyolefin containing a polar group and a compatibilizer has been proposed. However, it has been found that the use of such oligomers (e.g., polyolefins containing such compatibilizers or polar groups) reduces the mechanical properties or diminishes the thermal characteristics of the PPS.

Disclosure of Invention

Technical problem

Therefore, there is a need to develop a PAS composition having excellent metal adhesion, and having a reduced amount of outgassing in the flow front, which is a potential problem in conventional metal-adhered plastics, and having a small amount of by-products such as chlorine.

An object of the present invention is to provide a resin composition having excellent whiteness, acid resistance and metal adhesion, and generating a small amount of outgas in a flow front.

Further, another object of the present invention is to provide a molded article produced by subjecting the resin composition to casting molding.

Means for solving the problems

To achieve the above object, the present invention provides a resin composition comprising polyarylene sulfide and poly (cyclohexylenedimethylene terephthalate) comprising a repeating unit represented by formula 1, wherein the amount of outgas is 300ppm or less:

[ formula 1]

In addition, the invention also provides a molded product manufactured by casting and molding the resin composition.

The invention has the advantages of

The resin composition of the present invention has excellent metal adhesion properties without lowering excellent mechanical and thermal properties peculiar to PAS, with a small amount of outgas. Thus, various applications are possible, including electronic parts integrated by insert injection molding to automobile parts. In addition, the resin composition contains a small amount of by-products in the form of salts, and does not degrade the performance of electronic products, and can be used as an interior material of a cellular phone or a notebook computer without degrading the performance of electronic products. Further, the resin composition can achieve higher whiteness even after acid treatment, and can be applied as an exterior material in addition to an interior material.

Drawings

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

Best Mode for Carrying Out The Invention

The present invention provides a resin composition comprising polyarylene sulfide and poly (cyclohexylenedimethylene terephthalate) comprising a repeating unit represented by formula 1:

[ formula 1]

The resin composition of the present invention has a small amount of outgas of 300ppm or less, and can obtain excellent metal adhesion properties. Specifically, the resin composition has an air release amount of 150-300 ppm.

The resin composition has a chlorine content of 300ppm or less and includes a small amount of by-products in the form of salts, thereby not deteriorating the performance of electronic products. In particular, the resin composition has a chlorine content of 200ppm or less, 100ppm or less, for example, greater than 0 to less than or equal to 100ppm, more particularly, 50ppm or less.

The resin composition has a tensile strength value of 80MPa or more, particularly 80 to 150MPa, measured according to ISO 527.

The resin composition has a metal adhesion strength value of 60MPa or more, particularly 60 to 80MPa, as measured according to ASTM D3163.

Further, the resin composition has an L value of 89 or more, particularly 90 to 93, as measured in accordance with a specular component-included (SCI) mode of a D65 light source. The higher the value of L, the better the whiteness.

The resin composition has a metal adhesion strength value after anodizing of 55MPa or more, particularly 55 to 80MPa, as measured according to ASTM D3163.

The L value of the resin composition after anodic oxidation by a chemical method using an acid, measured according to SCI mode of D65 light source, is 88 or more, particularly 88 to 93.

Hereinafter, the present invention will be described in detail.

The resin composition of the present invention includes polyarylene sulfide.

The polyarylene sulfide includes iodine and free iodine bonded to its main chain, and particularly, the amount of iodine and free iodine bonded to the main chain may be 10 to 10,000 ppm. The amount of iodine bound to the main chain and free iodine can be measured by heat treating a polyarylene sulfide sample at high temperature and quantifying using ion chromatography. Free iodine is generated during the polymerization of a diiodo aromatic compound and elemental sulfur, and includes iodine molecules, iodide ions, iodine radicals, etc., and generally remains in a state of being chemically separated from the finally produced polyarylene sulfide.

Polyarylene sulfide can be prepared by melt polymerizing reactants comprising diiodo aromatic compound and elemental sulfur. The diiodo aromatic compound that can be used in the polymerization reaction may be at least one selected from the group consisting of Diiodobenzene (DIB), diiodonaphthalene, diiodobiphenyl, diiodobisphenol and diiodobenzophenone, but an embodiment of the present invention is not limited thereto. Further, the diiodo aromatic compound may include a diiodo aromatic compound in which a substituent alkyl group or a sulfone group is substituted, or a diiodo aromatic compound in which an atom such as oxygen and nitrogen is contained in an aromatic group. Further, the diiodo aromatic compound may have various isomers of diiodide depending on the bonding position of iodine element, and compounds in which iodine is bonded at the para-position, for example, p-diiodobenzene, 2, 6-diiodonaphthalene and 4,4' -diiodobiphenyl, are more suitable.

The form of the elemental sulfur reacted with the diiodo aromatic compound is not particularly limited. Elemental sulfur is typically present in the form of cyclooctathion (S8), in which 8 atoms are attached at room temperature. If not in this form, commercially available sulfur in solid or liquid form may be used without particular limitation.

In addition, the mixture of diiodo aromatic compound and reactant may further comprise a polymerization initiator, a stabilizer or a mixture thereof. The polymerization initiator may include at least one selected from the group consisting of 1, 3-diiodo-4-nitrobenzene, mercaptobenzothiazole, 2' -dithiobenzothiazole, cyclohexylbenzothiazole sulfenamide and butylbenzothiazole sulfenamide, but is not limited thereto.

The stabilizer may be used without any limitation as long as it is a stabilizer commonly used in resin polymerization.

Meanwhile, a polymerization quencher may be added during the melt polymerization. The polymerization quencher is not particularly limited as long as it can remove an iodine group contained in the polymerized polymer to stop the polymerization. Specifically, the polymerization quencher may be at least one selected from the group consisting of diphenyl sulfide, diphenyl ether, diphenyl benzophenone, dibenzothiazole disulfide, monoiodoaryl compounds, benzothiazole sulfenamide, thiurams (thiurams), and dithiocarbamates. More specifically, the polymerization quencher may be at least one selected from the group consisting of iodobiphenyl, iodophenol, iodoaniline, iodobenzophenone, 2-mercaptobenzothiazole, 2' -dithiobis-benzothiazole, N-cyclohexyl-2-benzothiazolesulfenamide, 2-morpholinothio-benzothiazole, N-dicyclohexyl-2-benzothiazolesulfenamide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate and diphenyldisulfide.

The injection point of the polymerization quencher can be determined in consideration of the molecular weight of the target polyarylene sulfide. For example, the polymerization quencher may be injected at a point when about 70 to 100 wt% of the diiodo aromatic compound contained in the initial reactants is consumed by the reaction.

Further, the conditions of the melt polymerization are not particularly limited as long as the polymerization of the reactants comprising the diiodo aromatic compound and the elemental sulfur can be initiated. For example, melt polymerization can be conducted under conditions of elevated temperature and reduced pressure. In this case, from the initial reaction conditions of 180-250 ℃ and 50-450 Torr, the temperature can be raised to 270-350 ℃ and the pressure can be lowered to the final reaction conditions of 0.001-20 Torr, and the reaction can be carried out for about 1-30 hours. More specifically, the polymerization reaction can be carried out under final reaction conditions of a temperature of about 280 ℃ and 300 ℃ and a pressure of about 0.1 to 1 torr.

Meanwhile, the method of preparing polyarylene sulfide may further include, before the melt polymerization: a step of melt-mixing reactants including a diiodo aromatic compound and elemental sulfur. The conditions for melt-mixing are not particularly limited as long as the reactants can be melt-mixed. For example, the melt mixing step can be performed at a temperature of 130 ℃ to 200 ℃, particularly 160 ℃ to 190 ℃. This melt mixing step prior to melt polymerization may allow the subsequent melt polymerization reaction to proceed easily.

In the method for preparing polyarylene sulfide according to another embodiment of the present invention, the melt polymerization may be performed in the presence of a nitrobenzene-based catalyst. Further, when a melt-mixing step is further performed before the above melt-polymerization reaction, a nitrobenzene-based catalyst may be added in the melt-mixing step. For example, nitrobenzene-based catalysts may include, but are not limited to, 1, 3-diiodo-4-nitrobenzene or 1-iodo-4-nitrobenzene.

Unlike the conventional production method, the polyarylene sulfide thus produced hardly generates a by-product in the form of a salt. For example, the polyarylene sulfide of the present invention has a chlorine content of 300ppm or less, specifically 200ppm or less, more specifically 100ppm or less.

The polyarylene sulfide may have a melting point of about 265 ℃ to about 290 ℃, about 270 ℃ to about 285 ℃, or about 275 ℃ to about 283 ℃. In addition, the polyarylene sulfide may have a number average molecular weight of about 5,000-. Further, the polyarylene sulfide may have a dispersity of about 2.0 to 4.5, about 2.0 to 4.0, or about 2.0 to 3.5, which is defined as a weight average molecular weight relative to a number average molecular weight.

The melt viscosity of the polyarylene sulfide measured at 300 ℃ with a rotary disk viscometer can be about 10-50,000 poise, about 100-20,000 poise, or about 300-10,000 poise.

Meanwhile, the resin composition of the present invention comprises poly (cyclohexylenedimethylene terephthalate) (PCT). The poly (cyclohexylenedimethylene terephthalate) comprises a repeating unit represented by the following formula 1.

[ formula 1]

The PCT comprising the repeating unit represented by formula 1 may have a weight average molecular weight of 10,000-200,000, or 30,000-70,000, and an Intrinsic Viscosity (IV) of 0.1 to 1dl/g, or 0.5 to 0.8 dl/g. In addition, the L value of the PCT was 80 or more, particularly 85 or more, when measured using a spectral colorimeter according to a mode including a specular reflection component of the D65 light source; the value of b is 10 or less, particularly 6 or less.

The PCT can be prepared by a conventional preparation method including the steps of injecting a catalyst containing a germanium compound into a mixture of a diol compound and a dicarboxylic acid and stirring to perform an esterification reaction and a polycondensation reaction.

The resin composition may include PCT in an amount of 0.5 to 50 parts by weight, 1 to 40 parts by weight, or 3 to 30 parts by weight, based on 100 parts by weight of PAS. In the case where the amount of PCT is 0.5 parts by weight or more based on 100 parts by weight of PAS, the metal adhesion and the whiteness may become excellent, and in the case where the amount of PCT is 50 parts by weight or less, deterioration of the mechanical strength of the resin composition may not occur.

According to an embodiment of the present invention, the resin composition can achieve excellent whiteness and metal adhesion, which cannot be achieved by conventional PAS resin compositions, and also can achieve high whiteness retention and high metal adhesion after anodizing.

In addition, the resin composition of the present invention may further include at least one component selected from the group consisting of phenoxy resins (phenoxy resins), elastomers, fillers, shock absorbers (shock absorbers), adhesion enhancers, stabilizers, pigments, plasticizers, lubricants and nucleating agents.

The resin composition may further include a phenoxy resin, and metal adhesion of the resin composition may be enhanced by further including the phenoxy resin. Specifically, the phenoxy resin may have a weight average molecular weight of 10,000-250,000 and a glass transition temperature of 50-130 ℃. More specifically, the phenoxy resin may be represented by the following formula 2. More specifically, the phenoxy resin may include bisphenol A (BPA), and may have a weight average molecular weight of 20,000-220,000 and a glass transition temperature of 60-120 ℃.

[ formula 2]

In formula 2, n is an integer of 100-. Specifically, n can be an integer of 100-.

The end of the phenoxy resin may be substituted with a hydroxyl group and/or a carboxyl group.

The resin composition may include the phenoxy resin in an amount of 1 to 75 parts by weight, based on 100 parts by weight of PAS. Particularly, the phenoxy resin may be added in an amount of 3 to 15 parts by weight, based on 100 parts by weight of PAS.

An elastomer may be additionally added to the resin composition of the present invention to impart toughness to the resin composition and to produce an effect of preventing interfacial separation between the resin and the metal due to a temperature change after adhesion to the metal. As the elastomer, at least one thermoplastic elastomer selected from the group consisting of polyvinyl chloride-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, polybutadiene-based elastomers, and terpolymers of glycidyl methacrylate, methacrylate and ethylene can be used. In particular, the elastomer may be a terpolymer of glycidyl methacrylate, methacrylate and ethylene.

The resin composition may include the elastomer in an amount of 1 to 75 parts by weight, particularly 3 to 35 parts by weight, based on 100 parts by weight of PAS.

As the filler, at least one selected from the group consisting of glass fiber, carbon fiber, boron fiber, glass bead, glass flake, talc and calcium carbonate can be used, and glass fiber is preferable. The glass fiber may be a silane-treated glass fiber, and the silane may be selected from epoxy silane and amino silane and a combination thereof, and particularly, an epoxy silane-treated glass fiber may be used.

The filler may be in the form of powder or flake, but is not limited thereto.

The filler may be contained in an amount of 5 to 250 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight of PAS.

The pigment may be an organic or inorganic pigment well known in the art and may be selected from, for example, zinc sulfide (ZnS), zinc oxide (ZnO), titanium dioxide (TiO)₂) And combinations thereof. In particular, the pigment may be zinc sulfide (ZnS).

The pigment may be contained in an amount of 0.1 to 50 parts by weight, preferably 0.3 to 25 parts by weight, based on 100 parts by weight of PAS.

The stabilizer may be, for example, an antioxidant, a light stabilizer, and combinations thereof. In addition, the stabilizer may be contained in an amount of 0.1 to 10 parts by weight, based on 100 parts by weight of PAS.

Examples of the antioxidant may include any material that can impart high heat resistance and heat stability to the resin composition without particular limitation. For example, phenolic antioxidants, aminic antioxidants, sulfur antioxidants and phosphorus antioxidants can be used. As the phenolic antioxidant, a hindered phenol compound is preferably used. Specific examples of the phenolic antioxidant include tetrakis (methylene-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate) methane, thiodiethylene bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], N' -bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, and the like. Examples of the phosphorus-based antioxidant include tris (2, 4-di-t-butylphenyl) phosphate, O' -octacosyl pentaerythritol bis (phosphite), bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, 3, 9-bis (2, 4-di-t-butylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane, and the like.

The light stabilizer may be any material that can absorb and block ultraviolet rays without particular limitation; and may be, for example, a benzophenone-based compound; salicylate-based compounds; a benzotriazole compound; acrylonitrile compounds; other compounds having an ultraviolet absorbing effect, such as conjugated compounds; a compound capable of trapping radicals, such as hindered amine compounds and hindered phenol compounds, or a combination thereof. If a compound having an ultraviolet absorbing effect and a compound capable of trapping radicals are used together, high ultraviolet absorbing and blocking effects can be obtained.

The resin composition may further comprise a lubricant for enhancing moldability. In particular, the hydrocarbon-based lubricant is useful for preventing friction between the resin and the mold metal, and allowing easy detachment from the mold (releasability), and the like. The hydrocarbon-based lubricant may be selected from paraffin wax, Polyester (PE) wax, polypropylene (PP) wax, oxidized polyester wax, and combinations thereof without particular limitation. Further, the lubricant may be added to the resin composition in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of PAS.

Meanwhile, the present invention can provide a molded article made of the above resin composition.

The resin composition may be cast-molded, for example, biaxially extruded, according to a method known in the art to produce a molded article having excellent metal adhesion, whiteness, and acid resistance, and may be used in various applications.

The molded article may have various forms including a film, a sheet or a fiber. The molded article may be an injection molded article, an extrusion molded article or a blow molded article. In the case of injection molding, the temperature of the mold may be about 130 ℃ or more in terms of crystallization. In the case where the molded articles are in the form of films, sheets, they may be formed into various films or sheets, for example, non-oriented, uniaxially oriented or biaxially oriented films or sheets. When the molded article is a fiber, the molded article can be used as a non-oriented fiber, a drawn fiber, an ultra-drawn fiber or the like, and also as a woven fabric, a knitted fabric, a nonwoven fabric (spunbonded fabric, meltblown fabric, staple fabric), a cord or a net.

The above molded articles can be used as coatings for electric or electronic parts such as computer fittings requiring metal adhesion, building materials, automobile parts, machine parts or basic goods, and areas in contact with chemicals or industrial fibers having chemical resistance.

Examples of the invention

The present invention will be described in more detail below with reference to embodiments. The following examples are intended to further illustrate the invention, but the scope of the invention is not limited thereto.

Preparation example: preparation of PPS

In a 5L reactor equipped with a thermocouple for measuring the temperature inside the reactor and vacuum lines for filling nitrogen and making vacuum, a mixture containing 5,130g of p-diiodobenzene (p-DIB) and 450g of sulfur was heated to 180 ℃ to be completely melted and mixed. The mixed reactants were polymerized by initiating the reaction at 220 ℃ and 350 torr, and gradually raising the temperature and lowering the pressure for 4 hours to the final conditions of 300 ℃ and 0.6-0.9 torr, and by injecting 7 times of sulfur and 19g each. When the polymerization reaction proceeded to about 80% (the degree of polymerization reaction was determined by "(current viscosity/target viscosity) × 100"), that is, the relative ratio of the current viscosity to the target viscosity. The current viscosity was measured by sampling during the polymerization, and the target viscosity was set to 2,000 poise), 35g of diphenyl disulfide was added as a polymerization quencher, and the reaction was carried out under a nitrogen atmosphere for 10 minutes. The pressure was reduced to 0.5 torr or less to gradually generate a vacuum, and the reaction was terminated after the target viscosity was reached to synthesize a polyarylene sulfide (PPS) resin having no hydroxyl group at the terminal of its main chain. The resin after the completion of the reaction was pelletized using a small pelletizer (small strand cutter).

The melting point (Tm), number average molecular weight (Mn), polydispersity index (PDI), and melt viscosity (to be referred to as "MV" hereinafter) of the PPS resin were measured by the following methods. As a result of the measurement, it was found that the Tm of the PPS resin was 280 ℃, Mn was 17,420, PDI was 2.8, MV was 2,150 poise, and the content of iodine bonded to the main chain and free iodine was 200 ppm.

Melting Point (Tm)

Melting points were measured using a Differential Scanning Calorimeter (DSC) while increasing the temperature from 30 ℃ to 320 ℃ at a rate of 10 ℃/min, cooling to 30 ℃, and then increasing the temperature from 30 ℃ to 320 ℃ at a rate of 10 ℃/min.

Number average molecular weight (Mn) and polydispersity index (PDI)

The PPS resin was dissolved in 1-chloronaphthalene to a concentration of 0.4 wt% by stirring at 250 ℃ for 25 minutes to prepare a sample. Thereafter, polyarylene sulfide having different molecular weights was flowed at a flow rate of 1mL/min and sequentially separated in a column of a high temperature Gel Permeation Chromatography (GPC) system (210 ℃), and an intensity corresponding to the molecular weight of the separated polyarylene sulfide was measured using an RI detector. After a calibration curve was prepared using a standard sample (polystyrene) of known molecular weight, the relative number average molecular weight (Mn) and polydispersity index (PDI) of the obtained PPS resin were calculated.

Melt viscosity (Melt viscocity, MV)

Melt viscosity was measured using a rotary disk viscometer at 300 ℃. When measured by the frequency sweep method, the angular frequency was measured to be 0.6 to 500rad/s, and the viscosity at 1.84rad/s was defined as the Melt Viscosity (MV).

Content (ppm) of iodine bonded to main chain and free iodine

The amounts (ppm) of backbone-bonded iodine and free iodine in the PPS resin were measured using a sample prepared by an automatic flash furnace (AQF) in which the PPS resin was burned at 1000 ℃ using a furnace and iodine was ionized and dissolved in distilled water, and a calibration curve previously analyzed by ion chromatography was used.

Example 1: preparation of PPS resin composition

To 100 parts by weight of the PPS resin obtained in preparation example, 9 parts by weight of a PCT resin (manufacturer: SK Chemicals, product name: 0302, weight average molecular weight: 56,000, Intrinsic Viscosity (IV): 0.65dl/g, and L value of 90 as measured using a spectral colorimeter in a mode including a specular component from a D65 light source), 9 parts by weight of a phenoxy resin (manufacturer: InChem Co., product name: PKHH, weight average molecular weight: 52,000, glass transition temperature: 92 ℃), 25 parts by weight of a glass fiber treated with epoxy silane (manufacturer: Owens corning Co., product name: V-910), 9 parts by weight of ZnS (manufacturer: Sachleben Co., product name: Sachtolith) as a white pigment, and 13 parts by weight of an elastomer (manufacturer: Arkema, product name: Lotader-8900, glycidyl methacrylate, and L-K) were added in a twin-screw extruder, A terpolymer of acrylic ester and ethylene) to prepare a PPS resin composition.

An extruder (SM Platek) having a diameter of 40mm and an L/D of 44 was used as a twin-screw extruder under conditions of a screw rotation speed of 250rpm, a feed rate of 60 kg/hr, a cylinder temperature of 280 ℃ and a torque of 60%. The raw materials were injected using three feeders, wherein the first feeder was used for dispersing and injecting the PPS resin, the PCT resin, the phenoxy resin, and the elastomer, the second feeder was used for dispersing and injecting the white pigment, and the third feeder was used for dispersing and injecting the glass fiber to prepare the PPS resin composition.

Examples 2 to 5 and comparative example 1

A PPS resin composition was prepared by following the same procedure as described in example 1, except that the components and the amounts thereof were as shown in Table 2 below.

Comparative example 2

A PPS resin composition was prepared by following the same procedure as described in example 1, except that PPS obtained by solution polymerization (manufacturer: Celanese Co., product name: 0205P4, linear PPS, which will be hereinafter referred to as "PPS 1") was used as the PPS resin in place of the PPS obtained in the preparation examples.

Comparative example 3

A PPS resin composition was prepared by following the same procedure as described in example 1, except that PPS obtained by solution polymerization (manufacturer: Solvay Co., product name: P6, crosslinked PPS, which will be hereinafter referred to as "PPS 2") was used as the PPS resin in place of the PPS obtained in the preparation example.

Comparative example 4

A PPS resin composition was prepared by following the same procedure as described in example 1, except that the components and the amounts thereof were as shown in Table 2 below, and no PCT resin was used.

Comparative example 5

Comparative example 6

A PPS resin composition was prepared by following the same procedure as described in example 1, except that polyethylene terephthalate (PET, manufacturer: SK Chemicals Co., product name: BB 8055) was used in place of the PCT resin.

The manufacturers of the components used in examples 1-5 and comparative examples 1-6 are summarized and shown in table 1 below.

[ Table 1]

Examples of the experiments

The physical properties of the PPS resin compositions prepared in examples and comparative examples were measured as follows. The results are shown in table 2 below.

First, the PPS resin compositions prepared in examples and comparative examples were injection-molded at 310 ℃ to prepare injection-molded specimens (injection molded parts).

(1) Gas release amount

An etched aluminum specimen (width: 70mm, length: 18mm, height: 2mm) was placed between the fixed mold and the moving mold of the two-step mold in the injection molding machine. Each of the PPS resin compositions prepared in examples and comparative examples was supplied to the two-step mold and inserted into an 80-ton Engel extruder at an injection rate of 50mm/s, an injection pressure of 120MPa, and a mold temperature of 150 ℃. Then, the test piece was separated from the mold to manufacture a test piece (width: 70mm, length 10mm, height: 3mm) for measuring the metal adhesion strength (FIG. 1). Thereafter, 2g of the injection molded specimen was placed in a 20mL sealed vial. After the vial was sealed, it was heated at 260 ℃ for 30 minutes using a Head Space (HS) apparatus, and the gas thus produced was automatically transferred to a gas chromatography-mass spectrometer (GC/MS) apparatus. Then, the components were separated by a capillary column for qualitative analysis, and the content of the components in the sample was quantitatively analyzed using benzothiazole as a standard substance.

(2) Chlorine content

50mg of each injection-molded sample of PPS of preparation example and the organic material of PPS1 or PPS2 (injection-molded sample of the above (1)) solution-polymerized were completely burned while being humidified at 1000 ℃ and the burned gas was collected into an absorption solution (900ppm of hydrogen peroxide) using an automatic flash oven (AQF). The resulting solution was automatically injected into an ion chromatograph, and the chlorine content of the injection molded sample was measured.

(3) Tensile strength

The tensile strength of the injection-molded test specimens was measured according to ISO 527 method.

(4) Strength of metal adhesion

The metal adhesion strength of the injection molded specimens was measured according to ASTM D3163.

(5) Value of L

The L value was measured using a spectral colorimeter (Konica Minolta, 3600D) according to the specular component reflection (SCI) -containing pattern of the D65 light source. The higher the value of L, the better the whiteness.

(6) Anodic oxidation reaction

The molded sample in the above (1) was immersed in a sodium hydroxide (NaOH) solution at 50 ℃ for 30 seconds and placed in a mixed solution of a 98 wt% sulfuric acid aqueous solution and a 84 wt% phosphoric acid aqueous solution at a volume ratio of 1:7 for 2 minutes. Thereafter, an oxidation process was performed by flowing a current of 20V in a dilute sulfuric acid solution at room temperature for 20 minutes, and a washing process was performed. The metal adhesion strength was measured by the same method as in (1), and the L value was measured by the same method as in (5), and the difference between these two values before and after the anodic oxidation was measured. It can be seen that the smaller the difference, the better the acidity.

[ Table 2]

As shown in Table 2, the resin composition of the present invention had a metal adhesion strength of 60 to 70MPa, and was significantly superior to that of 1 to 50MPa, which was the resin composition of comparative example 1 containing an excess of glass fiber. In addition, examples 1 to 5, which contained the PPS obtained in the preparation examples, exhibited about four times lower outgassing than comparative examples 2 and 3, which contained PPS1 or PPS 2. Further, examples 1 to 5 had a chlorine content of 35ppm or less, but comparative example 2 had a chlorine content higher and 891ppm, and comparative example 3 had a chlorine content of 1562 ppm. Further, for examples 1 to 5, the L value after the anodic oxidation was 90 or more, but that of comparative example 2 was 90 or less, and the whiteness thereof rapidly decreased.

Also, the resin compositions of examples 1 to 5 exhibited improved metal adhesion, and metal adhesion strength was 60 to 70MPa, when compared with comparative example 4, which did not contain PCT resin. However, the metal adhesion strength of comparative example 4 was 55MPa, and was very low.

In addition, comparative example 5, in which an excessive amount of PCT resin was added, had a decreased tensile strength. Meanwhile, comparative example 6, in which a PET resin instead of PCT resin was contained, exhibited high metal adhesion but low L value. This L value after anodization was significantly reduced compared to examples 1-5.

Therefore, the resin composition of the present invention exhibits reduced outgassing, excellent whiteness, acid resistance, and metal adhesion, and thus can be used in various fields including cellular phones, electronic parts, automobile parts, and the like, which can be integrated by insert injection molding.

Claims

1. A resin composition comprising a polyarylene sulfide and a poly (cyclohexylenedimethylene terephthalate) comprising a repeating unit represented by formula 1, and a filler, wherein the content of the filler is 10 to 150 parts by weight and the content of the poly (cyclohexylenedimethylene terephthalate) is 0.5 to 40 parts by weight based on 100 parts by weight of the polyarylene sulfide; the resin composition has an air release amount of 300ppm or less: the resin composition includes chlorine in an amount of 300ppm or less;

[ formula 1]

Wherein the gas release is measured by the following method: 2g of an injection-molded sample formed of the resin composition was placed in a 20mL sealed vial, heated at 260 ℃ for 30 minutes using a headspace device, the generated gas was automatically transferred to a gas chromatography-mass spectrometer device, the components were separated using a capillary column for qualitative analysis, and the content of the components in the sample was quantitatively analyzed using benzothiazole as a standard substance.

2. The resin composition as claimed in claim 1, wherein the weight average molecular weight of the poly (cyclohexylenedimethylene terephthalate) is 10000-200000.

3. The resin composition according to claim 1, wherein the polyarylene sulfide includes iodine bonded to its main chain or free iodine, and the amount of the iodine bonded to its main chain or the free iodine is 10 to 10000 ppm.

4. The resin composition according to claim 1, wherein the polyarylene sulfide includes chlorine in an amount of 300ppm or less.

5. The resin composition according to claim 1, further comprising at least one component selected from the group consisting of phenoxy resins, elastomers, vibration dampers, adhesion enhancers, stabilizers, pigments, plasticizers, lubricants and nucleating agents.

6. The resin composition as claimed in claim 5, wherein the phenoxy resin has a weight average molecular weight of 10000-250000 and a glass transition temperature of 50-130 ℃.

7. The resin composition of claim 5, wherein the phenoxy resin is represented by formula 2:

[ formula 2]

Wherein n is an integer of 100-900.

8. The resin composition according to claim 5, wherein the elastomer is at least one thermoplastic elastomer selected from the group consisting of polyvinyl chloride-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, and terpolymer elastomers of glycidyl methacrylate, and ethylene.

9. The resin composition according to claim 5, wherein the filler is at least one selected from the group consisting of glass fiber, carbon fiber, boron fiber, glass bead, glass flake, talc and calcium carbonate.

10. The resin composition of claim 9, wherein the glass fiber is a silane-treated glass fiber, wherein the silane is selected from one or more of an epoxy silane and an amino silane.

11. The resin composition according to claim 1, wherein the resin composition has a tensile strength value of 80MPa or more measured according to ISO 527.

12. The resin composition according to claim 1, wherein the resin composition has a metal adhesion strength value of 60MPa or more as measured according to ASTM D3163.

13. The resin composition according to claim 1, wherein the resin composition has an L value of 89 or more as measured in accordance with a SCI mode including a specular reflection component of a D65 light source.

14. The resin composition according to claim 1, wherein the resin composition has a metal adhesion strength value after anodic oxidation of 55MPa or more as measured according to ASTM D3163.

15. The resin composition according to claim 1, wherein the resin composition has an anodized L value of 88 or more as measured in accordance with a SCI mode including a specular reflection component of a D65 light source.

16. A molded article obtained by casting the resin composition according to any one of claims 1 to 15.

17. The molded article of claim 16, wherein the molded article is an electrical or electronic part requiring metal adhesion.

18. The molded article of claim 16, wherein the molded article is an automotive part requiring metal adhesion.