JP6707655B2 - Polyarylene sulfide composition having excellent adhesion to metals - Google Patents

Description

The present invention relates to polyarylene sulfide compositions with low outgassing and excellent whiteness, acid resistance and metal adhesion.

Polyarylene sulfide (hereinafter referred to as "PAS"), which is a typical engineering plastic at present, is used in high temperature and corrosive environments because of its high heat resistance, chemical resistance, fire resistance and electrical insulation. There is an increasing demand for various electric appliances and appliances. Polyphenylene sulfide (hereinafter referred to as "PPS") is the only commercially available polyarylene sulfide. PPS is widely used for the housing or key components of automotive equipment, electrical or electronic devices because of its excellent mechanical, electrical and thermal properties, and chemical resistance.

A widely used method for the commercial production of PPS is the combination of p-dichlorobenzene (hereinafter referred to as "pDCB") as a raw material and sodium sulfide in a polar organic solvent such as N-methylpyrrolidone. Solution polymerization, which is known as the Macallum process. However, when PPS is produced by the Macallum process, a solution polymerization method using sodium sulfide or the like may produce a by-product (for example, NaCl) in a salt form. Since such a by-product in the form of a salt may impair the performance of electronic components, further washing or drying method or the like is required to remove the by-product and residual organic solvent (US Pat. (See Nos. 2,513,188 and 2,583,941).

In order to solve the above problems, a method for preparing PAS, for example PPS, by melt polymerization of a reactant containing a diiodo aromatic compound and elemental sulfur has been proposed. Since the method does not produce by-products in salt form and does not use organic solvents during the preparation of PAS, it does not require a separate method to remove by-products or organic solvents.

On the other hand, in the conventional PPS, a large amount of released gas (low molecular weight oligomer) which prevents the filling of the micropores when adhering to the metal is generated in the injection flow front, which causes Since the adhesiveness decreases, there is a problem that the metal adhesiveness is low. As an alternative for improving the metal adhesion of PPS, a resin composition prepared by compounding PPS with a polyolefin containing a polar group and a compatibilizer has been proposed. However, the use of oligomers, such as compatibilizers or polyolefins containing polar groups, has been found to degrade or weaken the mechanical properties of PPS.

Technical challenges

Therefore, the PAS composition has excellent metal adhesion, reduces the amount of released gas at the flow front, which is a fundamental problem in conventional metal adhesive plastics, and has a small amount of by-products such as chlorine. It is necessary to develop things.

An object of the present invention is to provide a resin composition that has excellent whiteness, acid resistance and metal adhesion and that produces a small amount of released gas at the flow front.

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

Solution to the problem

To achieve the above object, the present invention provides a polyarylene sulfide and a compound of the formula:

A resin composition comprising a polycyclohexylene dimethylene terephthalate containing a repeating unit represented by, wherein the amount of released gas is 300 ppm or less.

Furthermore, the present invention provides a molded article produced by molding the above resin composition.

Advantageous effects of the invention

The resin composition according to the present invention has excellent metal adhesion properties with a small amount of outgassing, without degrading the excellent mechanical and thermal properties typical of PAS. Therefore, various applications including electronic parts to automobile parts that are integrated by injection insert molding may be possible. Furthermore, the resin composition contains a small amount of by-products in the form of a salt, and does not deteriorate the performance of the electronic product, and does not deteriorate the performance of the electronic product. It can be used as a material. Furthermore, the resin composition can achieve high whiteness even after acid treatment and may be applied as an exterior material in addition to the interior material.

FIG. 1 is a schematic view showing a part of a method for producing a sample for a metal bond strength test using the resin composition of the present invention.

The present invention comprises a polyarylene sulfide and a compound of formula 1:

There is provided a resin composition containing a polycyclohexylene dimethylene terephthalate containing a repeating unit represented by:

The resin composition of the present invention has a small amount of released gas of 300 ppm or less, and excellent metal adhesion performance can be achieved. Specifically, the resin composition may have a released gas amount of 150 to 300 ppm.

The resin composition has a chlorine content of 300 ppm or less and contains a small amount of by-products in the form of a salt, which does not deteriorate the performance of electronic products. In particular, the resin composition has a chlorine content of 200 ppm or less, 100 ppm or less, for example greater than 0 and 100 ppm or less, more particularly 50 ppm or less.

The resin composition may have a tensile strength value of 80 MPa or more, especially 80 to 150 MPa, measured according to ISO527.

The resin composition may have a metal adhesion strength value of 60 MPa or more, especially 60 to 80 MPa, measured according to ASTM D3163.

Furthermore, the resin composition has an L value of 89 or more, particularly 90 to 93, measured according to the (SCI: specular component-included) method. The higher the L value, the better the whiteness.

The resin composition may have a metal adhesion strength value of 55 MPa or more, especially 55 to 80 MPa, measured according to ASTM D3163 after anodization.

The resin composition may have an L value of 88 or more, in particular 88 to 93, measured according to the SCI method of a D65 light source, after anodizing by a chemical method using an acid.

Hereinafter, the present invention will be described in detail.

The resin composition of the present invention contains polyarylene sulfide.

The polyarylene sulfide comprises iodine and free iodine bound to its backbone, in particular the amount of iodine bound to the backbone and free iodine may be from 10 to 10,000 ppm. The amount of iodine and free iodine bound to the backbone may be measured by heat treating a polyarylene sulfide sample at elevated temperature and quantifying using ion chromatography. Free iodine is produced in the process of polymerizing a diiodo aromatic compound and elemental sulfur, and includes iodine molecules, iodine ions, iodine radicals, etc., and is generally chemically produced from the state of the finally produced polyarylene sulfide. It remains in a divided state.

The polyarylene sulfide may be prepared by melt polymerization of a reactant containing a diiodo aromatic compound and elemental sulfur. The diiodoaromatic compound that may be used in the polymerization reaction may be at least one selected from the group consisting of diiodobenzene (DIB), diiodonaphthalene, diiodobiphenyl, diiodobisphenol and diiodobenzophenone. However, the embodiments of the present invention are not limited thereto. Further, the diiodoaromatic compound may include a diiodoaromatic compound in which an alkyl group or a sulfone group is substituted as a substituent, or an atom such as oxygen and nitrogen is contained in the aromatic group. Further, the diiodo aromatic compound may have various isomers of the diiodo compound depending on the binding site of the iodine element, and a compound in which iodine is bound to the para position, such as p-diiodobenzene (pDIB). ), 2,6-diiodonaphthalene and p,p'-diiodobiphenyl are more suitable.

The form of elemental sulfur that reacts with the diiodoaromatic compound is not particularly limited. Generally, elemental sulfur exists at room temperature in the form of cycloocta sulfur (S ₈ ) with _eight atoms linked together. Commercially available sulfur that is not in such a form but is in solid or liquid form may be used without particular limitation.

Further, the mixture of the diiodo aromatic compound and the reactant may further contain a polymerization initiator, a stabilizer or a mixture thereof. The polymerization initiator is at least one selected from the group consisting of 1,3-diiodo-4-nitrobenzene, mercaptobenzothiazole, 2,2′-dithiobenzothiazole, cyclohexylbenzothiazolesulfenamide and butylbenzothiazolesulfenamide. However, it is not limited to these.

The stabilizer may be used without any limitation as long as it is a stabilizer generally used in the polymerization reaction of general resins.

On the other hand, a polymerization terminator may be added in the process of melt polymerization. The polymerization terminator is not particularly limited as long as it can terminate the polymerization by removing the iodine group contained in the polymer to be polymerized. Specifically, the polymerization terminator is at least one selected from the group consisting of diphenyl sulfide, diphenyl ether, diphenyl, benzophenone, dibenzothiazole disulfide, monoiodoaryl compound, benzothiazole, benzothiazole sulfenamide, thiuram and dithiocarbamate. May be More specifically, the polymerization terminator is iodobiphenyl, iodophenol, iodoaniline, iodobenzophenone, 2-mercaptobenzothiazole, 2,2′-dithiobisbenzothiazole, N-cyclohexylbenzothiazole-2-sulfenamide. , 2-morpholinothiobenzothiazole, N,N-dicyclohexylbenzothiazole-2-sulfenamide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate and diphenyldisulfide. It may be at least one.

The injection time of the polymerization terminator may be determined in consideration of the molecular weight of the target polyarylene sulfide. For example, the polymerization terminator may be injected at a time when about 70-100% by weight of the diiodoaromatic compound contained in the initial reactant is consumed by the reaction.

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

On the other hand, the method for preparing the polyarylene sulfide may further include a step of melt-mixing the reactant containing the diiodo aromatic compound and the elemental sulfur before the melt polymerization reaction. The conditions for melt mixing are not particularly limited, as long as the reactants can be melted and mixed. For example, the melt mixing step may be carried out at a temperature of 130 to 200°C, specifically 160 to 190°C. The melt-mixing step before melt-polymerization can facilitate the subsequent melt-polymerization.

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

The polyarylene sulfide prepared in this way hardly produces by-products in the form of salts, unlike the conventional preparation methods. For example, the polyarylene sulfides of the present invention have a chlorine content of 300 ppm or less, especially 200 ppm or less, more particularly 100 ppm or less.

The melting point of the polyarylene sulfide may be about 265-290°C, about 270-285°C or about 275-283°C. Further, the polyarylene sulfide may have a number average molecular weight of about 5,000 to 50,000, about 8,000 to 40,000 or about 10,000 to 30,000. Further, the polyarylene sulfide may have a dispersity of about 2.0-4.5, about 2.0-4.0 or about 2.0-3.5, where the dispersity is a number. It is defined as the weight average molecular weight relative to the average molecular weight.

The melt viscosity of the polyarylene sulfide measured at 300° C. with a rotating disc viscometer may be about 10-50,000 poise, about 100-20,000 poise or about 300-10,000 poise.

On the other hand, the resin composition of the present invention contains polycyclohexylene dimethylene terephthalate (PCT). Polycyclohexylene dimethylene terephthalate has the formula:

A repeating unit represented by

The PCT containing the repeating unit represented by Formula 1 has a weight average molecular weight of 10,000 to 200,000 or 30,000 to 70,000 and 0.1 to 1 dl/g or 0.5 to 0.8 dl/g. It may have an intrinsic viscosity (IV) of Furthermore, when using a spectrocolorimeter to measure by a method that includes specularly reflected light from a D65 light source, the PCT has an L value of 80 or more, especially 85 or more, and ab value of 10 or less, especially 6 or less.

PCT may be prepared by a general 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 the mixture to carry out 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. When the amount of PCT is 0.5 parts by weight or more with respect to 100 parts by weight of PAS, the metal adhesion and whiteness may be excellent, and when the amount is 50 parts by weight or less, the resin composition Deterioration of mechanical strength cannot occur.

According to the embodiments of the present invention, the resin composition can achieve excellent whiteness and metal adhesion which could not be achieved by the conventional PAS resin composition, and also the whiteness and metal adhesion after anodization. A high retention rate can be achieved.

Further, the resin composition of the present invention is at least one selected from the group consisting of a phenoxy resin, an elastomer, a filler, a shock absorber, an adhesion promoter, a stabilizer, a pigment, a plasticizer, a lubricant and a nucleating agent. May be further included.

The resin composition may further contain a phenoxy resin, and by further containing a phenoxy resin, the metal adhesion of the resin composition may be improved. In particular, the phenoxy resin may have a weight average molecular weight of 10,000 to 250,000 and a glass transition temperature of 50 to 130°C. More particularly, the phenoxy resin may be represented by the following formula 2. More particularly, the phenoxy resin may include bisphenol A (BPA) and may have a weight average molecular weight of 20,000 to 220,000 and a glass transition temperature of 60 to 120°C.

In Formula 2, n is an integer of 100 to 900. In particular, n may be an integer of 100 to 700, an integer of 100 to 500, an integer of 100 to 300, an integer of 200 to 300 or an integer of 300 to 500.

The terminals of the phenoxy resin may be substituted with hydroxyl groups and/or carboxyl groups.

The resin composition may include 1 to 75 parts by weight of phenoxy resin with respect to 100 parts by weight of PAS. In particular, the phenoxy resin may be added in an amount of 3 to 15 parts by weight with respect to 100 parts by weight of PAS.

Furthermore, in order to impart toughness to the resin composition and to bring about an effect of preventing separation of the interface between the resin and the metal due to a temperature change after adhesion with the metal, an elastomer is used as the resin composition of the present invention. May be added to. The elastomer is at least selected from the group consisting of polyvinyl chloride elastomer, polyolefin elastomer, polyurethane elastomer, polyester elastomer, polyamide elastomer, polybutadiene elastomer, and terpolymer of glycidyl methacrylate, methyl acrylic ester and ethylene. One type of thermoplastic elastomer may be used. In particular, the elastomer may be a terpolymer of glycidyl methacrylate, methyl acrylic ester and ethylene.

The resin composition may contain 1 to 75 parts by weight, especially 3 to 35 parts by weight of the elastomer, 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 beads, glass flake, talc and calcium carbonate may be used, and glass fiber is preferable. The glass fiber may be a silane-treated glass fiber, the silane may be selected from the group consisting of epoxysilane, aminosilane and combinations thereof, in particular epoxysilane-treated glass fiber may be used.

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

The filler may be included 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, for example selected from the group consisting of zinc sulfide (ZnS), zinc oxide (ZnO), titanium dioxide (TiO ₂ ) and combinations thereof. Good. In particular, the pigment may be zinc sulfide (ZnS).

The pigment may be included 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 included in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of PAS.

Examples of the antioxidant may include any material that can contribute to high heat resistance and thermal stability of the resin composition without particular limitation. For example, phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants and phosphorus-based antioxidants may be used. As the phenolic antioxidant, a hindered phenol compound is preferably used. Specific examples of phenolic antioxidants 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-hydroxyphenyl)propionamide], and the like. Examples of phosphorus-based antioxidants are tris(2,4-di-tert-butylphenyl)phosphate, O,O′-dioctadecylpentaerythritol bis(phosphite), bis(2,4-di-tert-butyl). Phenyl)pentaerythritol diphosphite, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxy-3,9-diphosphaspiro[5.5]undecane, etc. is there.

The light stabilizer is not particularly limited and may be any material capable of absorbing and blocking ultraviolet rays, for example, a benzophenone compound, a salicylate compound, a benzotriazole compound, an acrylonitrile compound, and an ultraviolet ray absorbing effect. Other compounds such as a conjugated compound, a compound capable of capturing a radical, such as a hindered amine compound and a hindered phenol compound, or a combination thereof may be used. When a compound having an ultraviolet absorbing effect and a compound capable of scavenging radicals are used at the same time, a high ultraviolet absorbing and blocking effect can be achieved.

The resin composition may further include a lubricant for improving moldability. In particular, a hydrocarbon-based lubricant may be used in order to prevent friction between the resin and the molding metal and to facilitate removal from the mold (release property). The hydrocarbon lubricant may be selected without particular limitation from the group consisting of paraffin wax, polyester (PE) wax, polypropylene (PP) wax, oxidized polyester wax, and combinations thereof. 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.

On the other hand, the present invention can provide a molded product produced from the above resin composition.

The resin composition may be molded by a method known in the art, for example, twin-screw extrusion, in order to produce a molded article having excellent metal adhesion, whiteness and acid resistance, and is used in various applications. May be used.

Molded articles may have various forms including films, sheets or fibers. 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 mold temperature may be about 130° C. or higher in terms of crystallization. When the shaped articles are in the form of films or sheets, they may be manufactured as 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 may be used as an unoriented fiber, drawn fiber or ultra-drawn fiber, etc., and also as a fabric, knit, non-woven fabric (spunbond, meltblown, staple), rope or net. May be used.

The above-mentioned moldings have electrical or electronic parts, such as computer accessories requiring metal adhesion, building materials, automobile parts, mechanical parts or basic daily necessities, as well as coatings or chemical resistance in the areas in contact with chemicals. It may be used as an industrial fiber.

Form of invention

Hereinafter, the present invention will be described in more detail with reference to embodiments. The following embodiments are intended to further illustrate the invention, without limiting the scope of the invention thereto.

Preparation Example: Preparation of PPS 5,130 g of p-diiodine in a 5 L reactor equipped with a thermocouple for measuring the internal temperature of the reactor and a vacuum line for filling with nitrogen and creating a vacuum. A mixture containing benzene (p-DIB) and 450 g of sulfur was heated to 180°C for complete melting and mixing. The reaction was started under the conditions of 220° C. and 350 torr, and the temperature was raised stepwise and the pressure was reduced over 4 hours to the final conditions of 300° C. and 0.6 to 0.9 torr, and sulfur was added. Polymerization was performed on the mixed reaction product by injecting 19 g each time 7 times. When the polymerization reaction progressed by about 80% (the polymerization reactivity was specified as “(current viscosity/target viscosity)×100”, that is, the relative ratio of the current viscosity to the target viscosity. The target viscosity was set at 2,000 poise), 35 g of diphenyl disulfide was added as a terminator and the reaction was carried out under a nitrogen atmosphere for 10 minutes. The pressure was reduced to 0.5 torr or less, a vacuum was gradually generated, the reaction was stopped after reaching a target viscosity, and a polyarylene sulfide (PPS) resin containing no hydroxyl group at the end of its main chain was synthesized. .. The resin after the termination of the reaction was molded into a pellet shape using a small strand cutter.

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

Melting point (Tm)
The temperature was raised from 30°C to 320°C at a rate of 10°C/min, cooled to 30°C, and then the temperature was raised from 30°C to 320°C at a rate of 10°C/min while the differential scanning calorimeter ( The melting point was measured using DSC).

Number average molecular weight (Mn) and polydispersity index (PDI)
Samples were prepared by dissolving the PPS resin in 1-chloronaphthalene with stirring at 250° C. for 25 minutes to a concentration of 0.4 wt %. Then, polyarylene sulfides having different molecular weights were caused to flow at a flow rate of 1 mL/min, and subsequently, they were separated in a column of a high temperature gel permeation chromatography (GPC) system (210° C.) to obtain the molecular weight of the separated polyarylene sulfide. The corresponding intensities were measured using a RI detector. The relative number average molecular weight (Mn) and polydispersity index (PDI) of the prepared PPS resin were calculated after creating a calibration curve using a standard sample (polystyrene) of known molecular weight.

Melt viscosity (MV)
Melt viscosity was measured at 300° C. using a rotating disk viscometer. In the measurement by the frequency sweep method, the angular frequency was measured as 0.6 to 500 rad/s, and the viscosity at 1.84 rad/s was defined as the melt viscosity (MV).

Amount of iodine and free iodine bound to the main chain (ppm)
Using a sample prepared by an automatic fast furnace (AQF), in which PPS resin was burned at 1,000° C. in a furnace, iodine was ionized, and dissolved in distilled water, and ion chromatography was used. A pre-analyzed calibration curve was used to determine the amount of backbone bound iodine and free iodine (ppm) in the PPS resin.

Example 1
Preparation of PPS resin composition In a twin-screw extruder, 9 parts by weight of PCT resin (manufacturer: SK Chemicals, product name: 0302, weight average molecular weight: 56 , 1,000, intrinsic viscosity (IV): 0.65 dl/g, L value: 90 measured by a method including specular reflection light of D65 light source using a spectrophotometer, 9 parts by weight of phenoxy resin (production) Supplier: InChem Co., product name: PKHH, weight average molecular weight: 52,000, glass transition temperature: 92° C., 25 parts by weight of glass fiber treated with epoxysilane (manufacturer: Owens Corning Co., product name : V-910), 9 parts by weight of ZnS as white pigment (manufacturer: Sachtleben Co., product name: Sachtolith) and 13 parts by weight of elastomer (manufacturer: Arkema Co., product name: Lotader AX-8900). , Glycidyl methacrylate, acrylic ester and ethylene terpolymer) were added to prepare a PPS resin composition.

As a twin-screw extruder, an extruder (SM Platek) having a diameter of 40 mm and L/D=44, a screw of 250 rpm, a feed rate of 60 kg/h, a barrel temperature of 280 to 300° C. and a torque of 60% was used. Used under conditions. Three feeders were used to inject the raw materials, each first feeder was used to disperse and inject PPS resin, PCT resin, phenoxy resin and elastomer, and the second feeder was white. A pigment was used to disperse and inject, and a third feeder was used to disperse and inject glass fiber to prepare a PPS resin composition.

Examples 2-5 and Comparative Example 1
Following the same procedure described in Example 1, using the ingredients and amounts set forth in Table 2 below, a PPS resin composition was prepared.

Comparative example 2
Except that PPS prepared by solution polymerization (manufacturer: Celanese Co., product name: 0205P4, linear PPS, hereinafter referred to as “PPS1”) is used as the PPS resin instead of the PPS prepared in Preparation Example. A PPS resin composition was prepared following the same procedure described in Example 1.

Comparative Example 3
Except that PPS prepared by solution polymerization (manufacturer: Solvay Co., product name: P6, crosslinked PPS, hereinafter referred to as “PPS2”) is used as the PPS resin instead of the PPS prepared in Preparation Example, A PPS resin composition was prepared following the same procedure described in Example 1.

Comparative Example 4
A PPS resin composition was prepared following the same procedure described in Example 1, except that the PCT resin was omitted and the components and amounts set forth in Table 2 below were used.

Comparative Example 5
A PPS resin composition was prepared following the same procedure described in Example 1 except that the ingredients and amounts set forth in Table 2 below were used.

Comparative Example 6
A PPS resin composition was prepared according to the same procedure described in Example 1 except that polyethylene terephthalate (PET, manufacturer: SK Chemicals Co., product name: BB8055) was used instead 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.

The physical properties of the PPS resin compositions prepared in Experimental 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 injected at 310° C. to prepare injection molded samples.

(1) Amount of released gas In the injection molding machine, an aluminum sample (width: 70 mm, length: 18 mm, height: 2 mm) etched between the fixed mold and the movable mold of the two-stage mold. I put it. Each PPS resin composition prepared in the examples and comparative examples was placed in a two-stage mold and placed in an 80 ton Engel extruder having an injection speed of 50 mm/s, an injection pressure of 120 MPa and a mold temperature of 150°C. Insert injection. After that, the sample was separated from the mold to manufacture a sample for measuring the metal adhesion strength (width: 70 mm, length 10 mm, height: 3 mm) (FIG. 1). Then, 2 g of injection molded sample was placed in a 20 mL sealed vial. After sealing the vial, it was heated for 30 minutes at 260° C. using a headspace (HS) device and the gas thus generated was automatically transferred to a gas chromatography-mass spectrometer (GC/MS) device. Moved. Then, each component was separated by a capillary column and qualitatively analyzed, and benzothiazole was used as a standard material to quantitatively analyze the amount of the component in the sample.

(2) Chlorine content Using an automatic fast reactor (AQF), 50 mg of each injection-molded PPS sample of Preparation Example and solution-polymerized PPS1 or PPS2 ((1) above injection molded). The sample) was completely burned at 1000° C. with humidification and the combustion gases were collected in an absorbing solution (900 ppm hydrogen peroxide). This solution was automatically injected into ion chromatography (AQF) and the amount of chlorine in the injection molded sample was measured.

(3) Tensile Strength The tensile strength of the injection molded sample was measured according to the method of ISO527.

(4) Metal Adhesion Strength The metal adhesion strength of the injection molded sample was measured according to ASTM D3163.

(5) L value The L value was measured using a spectrocolorimeter (Konica Minolta, 3600D) according to the (SCI) method that includes specularly reflected light from a D65 light source. The higher the L value, the better the whiteness.

(6) Anodizing Reaction The above-prepared molded sample (1) was immersed in a sodium hydroxide (NaOH) solution at 50° C. for 30 seconds, and 98% by weight of a sulfuric acid aqueous solution at a volume ratio of 1:7 and 84. The mixture was allowed to stand for 2 minutes in a mixed solution with a phosphoric acid aqueous solution of wt%. After that, an oxidizing method was carried out by flowing a current of 20 V in a dilute sulfuric acid solution at room temperature for 20 minutes, and a washing method was carried out. The metal adhesion strength was measured by the same method as (1), the L value was measured by the same method as (5), and the difference between the two values before and after anodization was measured. It can be recognized that the smaller the difference, the better the acidity.

As shown in Table 2, the metal adhesive strength of the resin composition according to the present invention is 60 to 70 MPa, which is more than 1 to 50 MPa of the resin composition according to Comparative Example 1 including an excessive amount of glass fiber. It was remarkably good. In addition, Examples 1-5 containing PPS prepared in Preparation Examples showed an emission gas content reduced by about 4 times when compared to the emission gas content of Comparative Examples 2 and 3 containing PPS1 or PPS2. Further, the chlorine content was 35 ppm or less in Examples 1 to 5, but was as high as 891 ppm in Comparative Example 2 and 1,562 ppm in Comparative Example 3. Furthermore, the L value after anodic oxidation was 90 or more in Examples 1 to 5, but 90 or less in Comparative Example 2, and the whiteness decreased sharply.

Further, the resin compositions of Examples 1 to 5 exhibited improved metal adhesion with a metal adhesion strength of 60 to 70 MPa as compared with Comparative Example 4 containing no PCT resin. However, the metal adhesion strength of Comparative Example 4 was 55 MPa, which was extremely low.

Furthermore, the tensile strength of Comparative Example 5 in which an excessive amount of PCT resin was added was lowered. On the other hand, Comparative Example 6 in which the PET resin was contained instead of the PCT resin showed high metal adhesion, but the L value was low. This L value was obviously lower than that of Examples 1 to 5 after anodizing.

Therefore, the resin composition of the present invention exhibits a reduced outgassing content, and excellent whiteness, acid resistance and metal adhesion, and is therefore suitable for mobile phones, electronic parts, automobile parts, etc. which are integrated by injection insert molding. It can be useful in various fields, including.
The inventions described in the claims at the time of filing of the present application will be additionally described below.
[1] Polyarylene sulfide and formula 1:
A resin composition comprising a polycyclohexylene dimethylene terephthalate containing a repeating unit represented by the formula (1), wherein the amount of released gas is 300 ppm or less.
[2] The resin composition according to [1], wherein the polycyclohexylene dimethylene terephthalate is contained in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of the polyarylene sulfide.
[3] The resin composition according to [1], wherein the polycyclohexylene dimethylene terephthalate has a weight average molecular weight of 10,000 to 200,000.
[4] The polyarylene sulfide contains iodine or free iodine bound to its main chain, and the amount of the iodine or free iodine bound to the main chain is 10 to 10,000 ppm, [1 ] The resin composition of description.
[5] The resin composition according to [1], wherein the polyarylene sulfide contains chlorine in an amount of 300 ppm or less.
[6] The resin composition is at least one selected from the group consisting of a phenoxy resin, an elastomer, a filler, a shock absorber, an adhesion promoter, a stabilizer, a pigment, a plasticizer, a lubricant and a nucleating agent. The resin composition according to [1], further including components.
[7] The resin composition according to [6], wherein the phenoxy resin has a weight average molecular weight of 10,000 to 250,000 and a glass transition temperature of 50 to 130°C.
[8] The phenoxy resin has the formula 2:
(In the formula, n is an integer of 100 to 900)
The resin composition according to [6], which is represented by:
[9] The elastomer is selected from the group consisting of polyvinyl chloride elastomer, polyolefin elastomer, polyurethane elastomer, polyester elastomer, polyamide elastomer, polybutadiene elastomer, and terpolymer elastomer of glycidyl methacrylate, methyl acrylic ester and ethylene. The resin composition according to [6], which is at least one thermoplastic elastomer selected.
[10] The resin composition according to [6], wherein the filler is at least one selected from the group consisting of glass fibers, carbon fibers, boron fibers, glass beads, glass flakes, talc and calcium carbonate.
[11] The resin composition according to [10], wherein the glass fiber is a silane-treated glass fiber, and the silane is selected from the group consisting of epoxysilane, aminosilane, and a combination thereof.
[12] The resin composition according to [1], wherein the resin composition contains chlorine in an amount of 300 ppm or less.
[13] The resin composition according to [1], wherein the resin composition has a tensile strength value of 80 MPa or more, measured according to ISO527.
[14] The resin composition according to [1], wherein the resin composition has a metal adhesion strength value of 60 MPa or more as measured according to ASTM D3163.
[15] The resin composition according to [1], wherein the resin composition has an L value of 89 or more when measured according to the (SCI) method that includes specular reflection light from a D65 light source.
[16] The resin composition according to [1], wherein the resin composition has a metal adhesive strength value of 55 MPa or more, measured according to ASTM D3163 after anodizing.
[17] The resin composition according to [1], which has an L value of 88 or more when measured according to the (SCI) method including specular reflection light of a D65 light source after the resin composition is anodized.
[18] A molded product produced by molding the resin composition according to any one of [1] to [17].
[19] The molded product according to [18], wherein the molded product is an electric or electronic component requiring metal adhesion.
[20] The molded product according to [18], which is an automobile part that requires metal adhesion.

Claims (18)

Polyarylene sulfide and formula 1:
A resin composition comprising a polycyclohexylene dimethylene terephthalate containing a repeating unit represented by, and a filler ,
A resin composition comprising the filler in an amount of 10 to 150 parts by weight based on 100 parts by weight of polyarylene sulfide, a chlorine content of 35 ppm or less, and an amount of released gas of 300 ppm or less. The resin composition according to claim 1, wherein the polycyclohexylene dimethylene terephthalate is included in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of the polyarylene sulfide. The resin composition according to claim 1, wherein the polycyclohexylene dimethylene terephthalate has a weight average molecular weight of 10,000 to 200,000. The polyarylene sulfide contains iodine or free iodine bound to its main chain, and the amount of the iodine bound to the main chain or the free iodine is 10 to 10,000 ppm. Resin composition. The resin composition further comprises at least one component selected from the group consisting of phenoxy resins, elastomers, shock absorbers , adhesion promoters, stabilizers, pigments, plasticizers, lubricants and nucleating agents. Item 2. The resin composition according to item 1. The resin composition according to claim 5 , wherein the phenoxy resin has a weight average molecular weight of 10,000 to 250,000 and a glass transition temperature of 50 to 130°C. The phenoxy resin has the formula 2:
(In the formula, n is an integer of 100 to 900)
The resin composition according to claim 5, which is represented by: The elastomer is selected from the group consisting of polyvinyl chloride elastomers, polyolefin elastomers, polyurethane elastomers, polyester elastomers, polyamide elastomers, polybutadiene elastomers, and terpolymer elastomers of glycidyl methacrylate, methyl acrylic ester and ethylene. The resin composition according to claim 5 , which is at least one thermoplastic elastomer. The resin composition according to claim 1 , wherein the filler is at least one selected from the group consisting of glass fibers, carbon fibers, boron fibers, glass beads, glass flakes, talc, and calcium carbonate. The resin composition according to claim 9 , wherein the glass fiber is a silane-treated glass fiber, and the silane is selected from the group consisting of epoxysilane, aminosilane, and combinations thereof. The resin composition according to claim 1, wherein the resin composition has a tensile strength value of 80 MPa or more, measured according to ISO527. The resin composition according to claim 1, wherein the resin composition has a metal adhesion strength value of 60 MPa or more, measured according to ASTM D3163. The resin composition according to claim 1, wherein the resin composition has an L value of 89 or more as measured according to a (SCI) method including specular reflection light of a D65 light source. The resin composition according to claim 1, wherein the resin composition has a metal adhesion strength value of 55 MPa or more, measured according to ASTM D3163 after anodizing. The resin composition according to claim 1, wherein the resin composition has an L value of 88 or more after being anodized and measured according to a (SCI) method including specular reflection light of a D65 light source. A molded article produced by molding the resin composition according to any one of claims 1 to 15 . The molded product according to claim 16 , wherein the molded product is an electric or electronic component requiring metal adhesion. The molded product according to claim 16 , wherein the molded product is an automobile part requiring metal adhesion.