WO2017142217A1 - Polyarylene sulfide composition having excellent adhesion to metals - Google Patents

Polyarylene sulfide composition having excellent adhesion to metals Download PDF

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Publication number
WO2017142217A1
WO2017142217A1 PCT/KR2017/000612 KR2017000612W WO2017142217A1 WO 2017142217 A1 WO2017142217 A1 WO 2017142217A1 KR 2017000612 W KR2017000612 W KR 2017000612W WO 2017142217 A1 WO2017142217 A1 WO 2017142217A1
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Prior art keywords
resin composition
resin
elastomers
weight
polyarylene sulfide
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PCT/KR2017/000612
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French (fr)
Korean (ko)
Inventor
김해리
신종욱
정명욱
안병우
오형근
Original Assignee
이니츠 주식회사
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Priority to JP2018543169A priority Critical patent/JP6707655B2/en
Priority to CN201780008608.0A priority patent/CN108603030B/en
Publication of WO2017142217A1 publication Critical patent/WO2017142217A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers

Definitions

  • the present invention relates to a polyarylene sulfide composition having a low content of outgas and excellent in whiteness, acid resistance and adhesion to a metal.
  • polyarylene sulfide (hereinafter referred to as 'PAS') is a representative engineering plastic, which is used in high temperature and corrosive environments due to high heat resistance, chemical resistance, flame resistance, and electrical insulation.
  • 'PAS' polyarylene sulfide
  • PPS polyphenylene sulfide
  • PAS such as PPS
  • melt-polymerizing a reactant containing a diiodine aromatic compound and elemental sulfur Since the PAS prepared by the melt polymerization method does not generate by-products in the form of salts during the manufacturing process and does not use an organic solvent, a separate process for removing by-products or organic solvents is not required.
  • the conventional PPS is unable to fill the fine pores of the metal surface due to the large amount of out gas (low molecular weight oligomer) generated in the injection flow front when bonding with the metal, thereby deteriorating the metal adhesion Occurred. Therefore, as an alternative to improve the adhesion between the PPS and the metal, a resin composition prepared by compounding a polyolefin containing a polar group and a compatibilizer with PPS has been proposed, but an oligomer such as a polyolefin containing such a compatibilizer or a polar group has been proposed. The use of has a problem of lowering the mechanical properties of PPS or weakening the thermal properties.
  • an object of the present invention is to provide a resin composition having a small amount of outgas generated at the flow front and excellent in whiteness, acid resistance and adhesion to metal.
  • Another object of the present invention is to provide a molded article produced by molding the resin composition.
  • PCT polycyclohexylenedimethylene terephthalate
  • the present invention also provides a molded article produced by molding the resin composition as described above.
  • the resin composition according to the present invention has a low out gas content without degrading the excellent mechanical and thermal properties peculiar to PAS and thus exhibits excellent metal adhesion performance. For this reason, the said resin composition can be applied to various uses in various fields from the electronic component integrated with injection insert molding to an automotive component.
  • the resin composition may contain a small amount of by-products in a salt form, and thus may not be deteriorated in the performance of electronic products.
  • the resin composition can be implemented as a high whiteness even after the acid treatment can be utilized as a material of the exterior material as well as interior materials.
  • Figure 1 illustrates a part of the process for producing a test piece for measuring the metal adhesive strength using the resin composition of the present invention.
  • the present invention is polyarylene sulfide; And it provides a resin composition comprising a polycyclohexylene dimethylene terephthalate comprising a repeating unit represented by the formula (1):
  • the resin composition of the present invention has a low out gas content of 300 ppm or less and shows excellent metal adhesion performance. Specifically, the resin composition may contain 150 to 300 ppm of outgas.
  • the resin composition has a chlorine content of 300 ppm or less and does not reduce the performance of the electronic product by including a small amount of by-products in the form of salt.
  • the chlorine content of the resin composition is 200 ppm or less, 100 ppm or less, for example, more than 0 to 100 ppm, more specifically 50 ppm or less.
  • the resin composition may have a tensile strength value of 80 MPa or more, specifically 80 to 150 MPa, measured according to ISO 527.
  • the resin composition may have a metal adhesive strength value of 60 MPa or more, specifically 60 to 80 MPa, measured according to ASTM D 3163.
  • the resin composition may have an L value of 89 or more, specifically 90 to 93, measured according to a specular component included (SCI) mode of the D65 light source.
  • SCI specular component included
  • the resin composition may have a metal adhesive strength value of 55 MPa or more, specifically 55 to 80 MPa, measured according to ASTM D 3163 after anodizing.
  • the resin composition may have an L value of 88 or more, specifically 88 to 93, measured according to the SCI mode of the D65 light source after anodizing by an acidic chemical method.
  • the resin composition of this invention contains polyarylene sulfide.
  • the polyarylene sulfide includes iodine and free iodine bonded to the main chain, and specifically, the content of iodine and free iodine bonded to the main chain may be 10 to 10,000 ppm.
  • the iodine and free iodine content bound to the main chain may be measured by quantitatively using ion chromatography after heat-treating a polyarylene sulfide sample at high temperature as described in the following Examples.
  • the free iodine occurs during the polymerization of the diiodine aromatic compound and the elemental sulfur, and refers to the iodine molecules, iodine ions, or iodine radicals, etc., which remain in a chemically separated state from the polyarylene sulfide finally formed.
  • the polyarylene sulfide may be prepared by melt polymerization of a reactant containing a diiodine aromatic compound and elemental sulfur.
  • Diiodine aromatic compounds that can be used for the polymerization reaction include diododobenzene (DIB), diiodonaphthalene, diiodobiphenyl, diiodobisphenol, and diiodophenol One or more selected from the group consisting of benzophenone (diiodobenzophenone), but is not limited thereto.
  • an alkyl group or a sulfone group may be bonded to the above-mentioned diiodine aromatic compounds with a substituent, or a diiodine aromatic compound in which atoms such as oxygen or nitrogen are contained in the aromatic group may also be used.
  • the diiodine aromatic compound has isomers of various diiodine compounds depending on the position of the iodine atom, among them, para-diiodobenzene (pDIB), 2,6-diiodonaphthalene, or p More suitable are compounds in which iodine is bonded in the para position, such as p'-diiodobiphenyl.
  • elemental sulfur which reacts with the said diiodine aromatic compound.
  • elemental sulfur is present in the form of a ring (cyclooctasulfur; S 8 ) having 8 atoms connected at room temperature. If it is not in this form, any commercially available solid or liquid sulfur may be used without particular limitation.
  • the mixture of the diiodine aromatic compound and the reactant may further include a polymerization initiator, a stabilizer, or a mixture thereof.
  • the polymerization initiator is 1,3-diiodo-4-nitrobenzene, mercaptobenzothiazole, 2,2'-dithiobenzothiazole, cyclohexylbenzothiazole sulfenamide, and butylbenzothiazole sulfenamide. It may include one or more selected from the group consisting of, but is not limited to the above examples.
  • the stabilizer is not particularly limited as long as it is a stabilizer usually used for polymerization of the resin.
  • a polymerization terminator may be added during the melt polymerization of the mixture.
  • the polymerization inhibitor is not particularly limited as long as it is a compound capable of stopping the polymerization by removing the iodine group contained in the polymer to be polymerized.
  • diphenyl sulfide, diphenyl ether, diphenyl, diphenyl, benzophenone, dibenzothiazole disulfide, and monoiodoaryl compound Benzothiazoles, benzothiazole sulfenamides, thiurams, and dithiocarbamates may be one or more selected from the group consisting of.
  • the polymerization terminator is iodobiphenyl (iodobiphenyl), iodophenol (iodophenol), iodoaniline (iodoaniline), iodobenzophenone (iodobenzophenone), 2-mercaptobenzothiazole (2-mercaptobenzothiazole) , 2,2'-dithiobisbenzothiazole, N-cyclohexylbenzothiazole-2-sulfenamide, 2-morpholinothiobenzothia 2-morpholinothiobenzothiazole, N, N-dicyclohexylbenzothiazole-2-sulfenamide, tetramethylthiuram monosulfide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide (tetramethylthiuram disulfide), zinc dimethyldithiocarbamate (Zinc dimethyldithiocarbamate),
  • the timing of administration of the polymerization terminator may be determined in consideration of the molecular weight of the polyarylene sulfide to be polymerized. For example, about 70 to 100% by weight based on the diiodine aromatic compound included in the initial reactant may be administered when the reaction is exhausted.
  • melt polymerization as mentioned above is not specifically limited as long as it can start the superposition
  • the melt polymerization may be performed at elevated temperature and reduced pressure conditions, in which case, the final reaction conditions of 270 to 350 ° C. and temperature rise and pressure drop are performed at initial reaction conditions of 180 to 250 ° C. and 50 to 450 torr. The amount can be changed to 0.001 to 20 torr, and can proceed for about 1 to 30 hours.
  • the polymerization reaction may be carried out at a final reaction condition of about 280 to 300 ° C. and about 0.1 to 1 torr of pressure.
  • the method for preparing polyarylene sulfide may further include melt mixing a reactant including a diiodine aromatic compound and elemental sulfur before the melt polymerization.
  • melt mixing is not particularly limited as long as the mixture can be melt mixed. For example, it may proceed at a temperature of 130 to 200 °C, or 160 to 190 °C.
  • the melt mixing step is performed before the melt polymerization, subsequent melt polymerization can be performed more easily.
  • the melt polymerization may be performed in the presence of a nitrobenzene catalyst.
  • the nitrobenzene-based catalyst may be added in the melt mixing step.
  • the nitrobenzene-based catalyst may include 1,3-diiodo-4-nitrobenzene, or 1-iodo-4-nitrobenzene, but is not limited thereto.
  • polyarylene sulfides prepared as described above produce little by-products in salt form, unlike conventional manufacturing processes.
  • the polyarylene sulfide of the present invention may have a chlorine content of 300 ppm or less, specifically 200 ppm or less, more specifically 100 ppm or less.
  • the polyarylene sulfide may have a melting point of about 265 to 290 ° C, about 270 to 285 ° C, or about 275 to 283 ° C.
  • the number average molecular weight may be about 5,000 to 50,000, about 8,000 to 40,000, or about 10,000 to 30,000.
  • the polyarylene sulfide may have a dispersion degree defined as a weight average molecular weight with respect to the number average molecular weight, about 2.0 to 4.5, about 2.0 to 4.0, or about 2.0 to 3.5.
  • the polyarylene sulfide may have a melt viscosity of about 10 to 50,000 poise, about 100 to 20,000 poise, or about 300 to 10,000 poise, measured at 300 ° C. with a rotating disc viscometer.
  • the resin composition of this invention contains polycyclohexylenedimethylene terephthalate.
  • the polycyclohexylenedimethylene terephthalate includes a repeating unit represented by the following formula (1).
  • PCT including a repeating unit represented by Formula 1 may have a weight average molecular weight of 10,000 to 200,000, or 30,000 to 70,000, intrinsic viscosity (IV) of 0.1 to 1 dl / g, or 0.5 to 0.8 dl / g Can be.
  • the PCT may have an L value of 80 or more, specifically 85 or more, and a b value of 10 or less, specifically 6 or less, measured in a specular colorimeter using a specular colorimeter with a specular spectrophotometer.
  • the PCT may be prepared by a conventional manufacturing method including adding a catalyst containing a germanium compound to a mixture of a diol compound and a dicarboxylic acid, stirring the same, and performing an esterification reaction and a polycondensation reaction.
  • the resin composition may include 0.5 to 50 parts by weight, 1 to 40 parts by weight, or 3 to 30 parts by weight of PCT based on 100 parts by weight of PAS.
  • PCT is included in an amount of 0.5 parts by weight or more based on 100 parts by weight of PAS, the metal adhesion and whiteness are excellent.
  • the resin composition contains PCT, the resin composition exhibits excellent whiteness and metal adhesion that the conventional PAS resin composition could not have, and also maintains the whiteness and metal adhesion after anodizing. High.
  • the resin composition of the present invention may further include one or more components selected from the group consisting of phenoxy resins, elastomers, fillers, shock absorbers, adhesion enhancers, stabilizers, pigments, plasticizers, lubricants and nucleating agents.
  • the resin composition may further include a phenoxy resin, and may further include a phenoxy resin to improve metal adhesion of the resin composition.
  • 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 specifically, the phenoxy resin may be represented by the following formula (2). More specifically, the phenoxy resin may include bisphenol A (bisphenol A, BPA), the weight average molecular weight is 20,000 to 220,000, the glass transition temperature may be 60 to 120 °C.
  • n is an integer of 100 to 900. Specifically, 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 phenoxy resin may be substituted at the terminal with a hydroxyl group and / or a carboxyl group.
  • the resin composition may include 1 to 75 parts by weight of phenoxy resin based on 100 parts by weight of PAS. Specifically, the phenoxy resin may be added in an amount of 3 to 15 parts by weight based on 100 parts by weight of PAS.
  • the elastomer may be, for example, a polyvinyl chloride elastomer, a polyolefin elastomer, a polyurethane elastomer, a polyester elastomer, a polyamide elastomer, a polybutadiene elastomer, a glycidyl methacrylate, methyl acrylic ester, or ethylene.
  • thermoplastic elastomers selected from the group consisting of terpolymer copolymers, specifically, terpolymer copolymer elastomers of glycidyl methacrylate, methyl acrylic ester and ethylene.
  • the resin composition may include 1 to 75 parts by weight, specifically 3 to 35 parts by weight of elastomer, based on 100 parts by weight of PAS.
  • the filler may be, for example, one or more selected from the group consisting of glass fibers, carbon fibers, boron fibers, glass beads, glass flakes, talc, talc and calcium carbonate, specifically, may be glass fibers.
  • the glass fiber may be a glass fiber treated with a silane selected from the group consisting of epoxy silane, amino silane and combinations thereof, and specifically, may be glass fiber treated with epoxy silane.
  • the filler may be in the form of powder or flake, but is not particularly limited thereto.
  • the resin composition may include 5 to 250 parts by weight, specifically 10 to 150 parts by weight of filler, based on 100 parts by weight of PAS.
  • the pigment may be any of a variety of conventional organic or inorganic pigments known in the art and may be selected, for example, from the group consisting of zinc sulfide (ZnS), zinc oxide (ZnO), titanium dioxide (TiO 2 ) and combinations thereof. have. Specifically, the pigment may be zinc sulfide (ZnS).
  • the pigment may be added in an amount of 0.1 to 50 parts by weight, specifically 0.3 to 25 parts by weight, based on 100 parts by weight of PAS.
  • the stabilizer examples include antioxidants, light stabilizers, combinations thereof, and the like.
  • the stabilizer may be added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of PAS.
  • the antioxidant is not particularly limited as long as it can play a role of supporting high heat resistance and thermal stability of the resin composition, and examples thereof include a phenol-based, amine-based, sulfur-based or phosphorus-based antioxidant.
  • the phenolic antioxidant may be, for example, a hindered phenolic compound, and specific examples thereof may be tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].
  • the phosphorus antioxidants include, for example, 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-tetraoxa-3,9-diphosphaspiro [5.5] undecane Etc. can be mentioned.
  • the light stabilizer is not particularly limited as long as it can act as a UV absorbing and blocking, for example, benzophenone compound, salicylate compound, benzotriazole compound, acryl UV-absorbing compounds such as nitrile compounds, other resonance structure compounds, and the like, and have a radical trapping ability such as hindered amine compounds and hindered phenol compounds. Compounds, combinations thereof, and the like can be used. In addition, when a compound having a UV absorbing effect and a compound having a radical trapping ability are used together, a higher UV absorbing and blocking effect can be obtained.
  • the resin composition may further include a lubricant, and in particular, a hydrocarbon-based lubricant may be used to prevent friction between the resin and the metal of the mold and to provide easy detachability (releasability) in the mold.
  • a hydrocarbon-based lubricant is not particularly limited, but may be selected from the group consisting of, for example, paraffin wax, polyester (PE) wax, polypropylene (PP) wax, oxidized polyester wax, and combinations thereof.
  • the lubricant may be added to the resin composition in an amount of 0.1 to 10 parts by weight, specifically 0.5 to 5 parts by weight based on 100 parts by weight of PAS.
  • this invention can provide the molded article manufactured from the said resin composition.
  • the resin composition as described above may be molded by a method known in the art such as biaxial extrusion to produce a molded article having excellent metal adhesion, whiteness and acid resistance, which can be applied to various applications.
  • the molded article may be in various forms such as a film, a sheet, or a fiber, and may be an injection molded article, an extrusion molded article, or a blow molded article.
  • the mold temperature in the case of injection molding may be 130 degreeC or more from a viewpoint of crystallization.
  • the molded article when it is in the form of a film or sheet, it can be produced into various films or sheets by using methods such as unstretched, uniaxial stretch, biaxial stretch, and the like.
  • the molded article is a fiber, it may be various fibers such as undrawn yarn, drawn yarn, or super drawn yarn, and may be used as a woven fabric, knitted fabric, nonwoven fabric (spunbond, melt blown, staple), rope, or net.
  • Such molded articles may be used as coatings for electrical or electronic parts, such as computer accessories requiring metal adhesive properties, building members, automobile parts, mechanical parts, daily necessities or chemical contact parts, industrial chemical resistant fibers, and the like.
  • a mixture containing 5,130 g of para-diiobenzene (p-DIB) and 450 g of sulfur in a 5 L reactor equipped with a thermocouple capable of measuring internal temperature of the reactor and a vacuum line capable of filling with nitrogen and vacuuming was charged at 180 ° C.
  • the final reaction temperature is 300 °C
  • the pressure is 0.6 to 0.9 Torr step by step temperature rise and pressure drop for 4 hours
  • 19 g of sulfur each time was added seven times to proceed with the polymerization.
  • the polyarylene sulfide (PPS) resin having no hydroxyl group at the end of the main chain was synthesized. Resin was completed was prepared in pellet form using a small strand cutter.
  • the resulting PPS resin was measured for melting point (Tm), number average molecular weight (Mn), molecular weight distribution (PDI) and melt viscosity (hereinafter referred to as 'MV') in the following manner.
  • Tm melting point
  • Mn number average molecular weight
  • PDI molecular weight distribution
  • 'MV' melt viscosity
  • DSC differential scanning calorimeter
  • Mn Number average molecular weight (Mn) and molecular weight distribution (PDI)
  • a sample in which PPS resin was dissolved in 1-chloronaphthalene (1-chloronaphthalene) at a concentration of 0.4% by weight at 250 ° C. for 25 minutes was prepared. Then, the polyarylene sulfides having different molecular weights were sequentially separated in the column while flowing the sample to a high temperature gel permeation chromatography (GPC) system 210 at a flow rate of 1 ml / min. Thereafter, the RI detector was used to measure the intensity of each of the polyarylene sulfides separated by molecular weight, and a calibration curve was prepared from polystyrene. The number average molecular weight (Mn) of the prepared PPS resin was prepared. And molecular weight distribution (PDI).
  • Mn number average molecular weight
  • PDI molecular weight distribution
  • melt viscosity was measured at 300 ° C. with a rotating disk viscometer. In measuring by the frequency sweep method, the angular frequency was measured from 0.6 rad / s to 500 rad / s, and the viscosity at 1.84 rad / s was defined as the melt viscosity (MV).
  • the main chain-bound iodine and free iodine content was measured by ion chromatography using an automatic pretreatment device (AQF) in which PPS resin was burned using a furnace at 1,000 ° C and ionized and dissolved in distilled water.
  • the content of iodine in the PPS resin was measured using a calibration curve analyzed in advance.
  • PCT resin (manufacturer: SK chemicals, product name: 0302, weight average molecular weight: 56,000, intrinsic viscosity (IV): 0.65 dl / g, spectroscopic side L value measured in a specular reflection mode of a D65 light source using a colorimeter: 90) 9 parts by weight, phenoxy resin (manufacturer: InChem, product name: PKHH, weight average molecular weight: 52,000, glass transition temperature: 92 ° C) 9 Parts by weight, 25 parts by weight of an epoxysilane-treated glass fiber (manufacturer: Owens corning, product name: V-910), 9 parts by weight of ZnS (manufacturer: Sachtleben, product name: Sachtolith) as a white pigment, elastomer (manufacturer: Arkema) , Product name: Lotader AX-8900, tertiary copolymer of glycidyl methacrylate, acrylic ester and
  • a PPS resin composition was prepared in the same manner as in Example 1, using the ingredients and contents as described in Table 2 below.
  • the composition was prepared.
  • PPS was prepared in the same manner as in Example 1, except that PPS prepared by solution polymerization instead of PPS in Preparation Example (manufacturer: Solvay, product name: P6, cross-linked PPS, described below as "PPS2") was used. A resin composition was prepared.
  • a PPS resin composition was prepared in the same manner as in Example 1, except that no PCT resin was used, using the ingredients and contents as described in Table 2 below.
  • a PPS resin composition was prepared in the same manner as in Example 1, using the ingredients and contents as described in Table 2 below.
  • a PPS resin composition was prepared in the same manner as in Example 1, except that polyethylene terephthalate (PET) resin (manufacturer: SK Chemical, product name: BB 8055) was used instead of PCT resin.
  • PET polyethylene terephthalate
  • Table 1 summarizes the availability of the components used in Examples 1 to 5 and Comparative Examples 1 to 6.
  • injection specimens were prepared by injecting the PPS resin compositions prepared in Examples and Comparative Examples at 310 ° C., respectively.
  • a specific etched aluminum specimen (width: 70 mm, length: 18 mm and height: 2 mm) was seated between the stationary mold and the moving mold of the injection molding machine two-stage mold.
  • insert injection was performed at an injection speed of 50 mm / s, an injection pressure of 120 MPa and a mold temperature of 150 ° C. in an 80 ton Engel injection machine, and then separated from the mold.
  • Specimens for measuring metal adhesion strength 70 mm wide, 10 mm long and 3 mm high) were prepared (FIG. 1).
  • the injection specimen (2 g) was put into a 20 ml sealed vial and sealed, and the gas generated after heating for 30 minutes at 260 ° C. with a HS (Head Space) equipment was automatically gas chromatography-mass spectrometer (GC / MS). Sent to the equipment. Thereafter, each component was separated by a capillary column and qualitatively analyzed, and benzothiazole was used as a standard substance to quantitatively analyze the content of each component in the sample.
  • HS Head Space
  • injection specimen of (1) 50 mg of PPS, solution-polymerized PPS1 or PPS2 resin of the preparation example (injection specimen of (1)) was humidified at 1,000 ° C. using AQF (Auto Quick Furnace) while completely burning the organic matter and absorbing the combustion gas. After collecting in 900 ppm hydrogen peroxide solution, the chlorine content of the injection specimen was measured after auto-injection by ion chromatography (ion chromatography, Auto Quick Furnace).
  • the tensile strength of the injection specimen of (1) was measured.
  • the metal adhesive strength of the injection specimen of (1) was measured according to the ASTM D 3163 method.
  • L value was measured according to the specular component included (SCI) mode of the D65 light source using a spectrophotometer (Konica Minolta, 3600D). The higher the L value, the better the whiteness.
  • the specimen molded in (1) was immersed in a 50 ° C. sodium hydroxide (NaOH) solution for 30 seconds, and then mixed in a solution containing 98% by weight sulfuric acid solution and 84% by weight phosphoric acid solution in a 1: 7 volume ratio for 2 minutes. Stayed. Thereafter, a 20 V current is passed in a dilute sulfuric acid solution at room temperature, followed by an oxidation process for 20 minutes, and then washed with water. Thereafter, the metal adhesive strength was measured in the same manner as in (1), and the L value was measured in the same manner as in (5), and then the difference between the two values before and after the anodic oxidation process was measured. The smaller the difference, the better the acid resistance.
  • NaOH sodium hydroxide
  • the resin composition which concerns on this invention showed the metal adhesive strength remarkably superior to 50 MPa of the comparative example 1 which contains an excess glass fiber with metal adhesive strength of 60-70 MPa.
  • Examples 1 to 5 including PPS prepared in Preparation Example showed an out gas content up to about 4 times lower than Comparative Examples 2 and 3 including PPS1 or PPS2.
  • the chlorine content was remarkably high while Examples 1 to 5 were 35 ppm or less, while Comparative Example 2 was 891 ppm and Comparative Example 3 was 1562 ppm.
  • Comparative Example 4 which does not contain PCT resin
  • the resin compositions of Examples 1 to 5 exhibited improved metal adhesive strength of 60 to 70 MPa, and Comparative Example 4 was 55 MPa. The strength was significantly lower.
  • Comparative Example 5 in which the PCT resin was added in excess, confirmed that the tensile strength decreased.
  • Comparative Example 6 containing a PET resin instead of PCT resin has a high metal adhesion capacity, but the L value was low, the L value was significantly lower than the Examples 1 to 5 after the oxidation process.
  • the resin composition according to the present invention exhibits excellent whiteness, acid resistance and metal adhesion while reducing outgas content, and thus can be usefully used in various fields such as mobile phones, electronic parts, automobile parts, etc., which are integrated with injection insert molding. .
  • impurities are not contained, deterioration of the performance of the electronic product can be prevented.

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Abstract

The present invention relates to a polyarylene sulfide composition having a low out-gas content, and having excellent brightness, acid resistance and adhesion to metals. The polyarylene sulfide resin composition of the present invention exhibits excellent brightness, acid resistance and metal adhesive strength as well as a low out-gas content, and thus can be useful as a resin composition for manufacturing a product requiring molding precision.

Description

금속과의 접착성이 우수한 폴리아릴렌 설파이드 조성물Polyarylene sulfide composition excellent in adhesion with metal
본 발명은 아웃 가스의 함량이 적고, 백색도, 내산성 및 금속과의 접착성이 우수한 폴리아릴렌 설파이드 조성물에 관한 것이다.The present invention relates to a polyarylene sulfide composition having a low content of outgas and excellent in whiteness, acid resistance and adhesion to a metal.
현재 폴리아릴렌 설파이드(polyarylene sulfide; 이하 'PAS'로 기재)는 대표적인 엔지니어링 플라스틱(engineering plastic)으로, 높은 내열성과 내화학성, 내화염성(flame resistance), 전기 절연성 등으로 인해 고온과 부식성 환경에서 사용되는 각종 제품이나 전자 제품에 사용되는 용도로 수요가 증대되고 있다. 이러한 폴리아릴렌 설파이드 중에서 상업적으로 판매되는 것은 폴리페닐렌 설파이드(polyphenylene sulfide, PPS)가 유일하다. PPS는 뛰어난 기계적, 전기적 및 열적 특성과 내약품성으로 인하여 자동차 장비, 전기 전자 기기의 하우징이나 주요 부품으로 널리 사용되고 있다.Currently, polyarylene sulfide (hereinafter referred to as 'PAS') is a representative engineering plastic, which is used in high temperature and corrosive environments due to high heat resistance, chemical resistance, flame resistance, and electrical insulation. There is an increasing demand for use in various products and electronic products. The only commercially available polyarylene sulfide is polyphenylene sulfide (PPS). PPS is widely used as a housing or major component of automotive equipment, electrical and electronic devices because of its excellent mechanical, electrical and thermal properties and chemical resistance.
현재까지 주로 적용되는 PPS의 상업적 생산 공정은, 파라-디클로로벤젠(p-dichlorobenzene, pDCB)과 황화나트륨(sodium sulfide)을 원료로 하여 N-메틸 피롤리돈(N-methyl pyrrolidone) 등의 극성 유기 용매에서 용액중합반응시키는 방법으로, 상기 방법은 맥컬럼 공정(macallum process)으로 알려져 있다. 이러한 맥컬럼 공정으로 제조한 PPS의 경우, 황화나트륨 등을 사용한 용액중합 공정으로 인해 염 형태의 부산물(예컨대, NaCl)이 발생할 수 있다. 이러한 염 형태의 부산물은 전자부품의 성능을 저하시키므로 반드시 제거해야 하며, 상기 부산물 및 유기용매의 제거를 위해 추가의 세척 또는 건조 공정 등이 필요하게 되는 단점이 있다(미국특허 제 2,513,188 호 및 제 2,583,941 호 참고).The commercial production process of PPS mainly applied to date is polar organic such as N-methyl pyrrolidone based on para-dichlorobenzene (pDCB) and sodium sulfide as raw materials. As a method of solution polymerization in a solvent, the method is known as a macallum process. In the case of PPS prepared by the MacColumm process, a by-product (eg, NaCl) in the form of a salt may occur due to a solution polymerization process using sodium sulfide or the like. These by-products in the form of salts must be removed because they deteriorate the performance of the electronic components, and there is a disadvantage that an additional washing or drying process is required to remove the by-products and the organic solvent. Reference).
이로 인해, 디요오드 방향족 화합물과 황 원소를 포함하는 반응물을 용융중합하는 방법으로 PPS 등의 PAS를 제조하는 대안이 제안되었다. 상기 용융중합법으로 제조된 PAS는 제조 과정 중에 염 형태의 부산물 등이 발생하지 않고 유기 용매를 사용하지 않으므로, 부산물이나 유기 용매의 제거를 위한 별도의 공정이 요구되지 않는다.For this reason, an alternative for producing PAS such as PPS has been proposed by melt-polymerizing a reactant containing a diiodine aromatic compound and elemental sulfur. Since the PAS prepared by the melt polymerization method does not generate by-products in the form of salts during the manufacturing process and does not use an organic solvent, a separate process for removing by-products or organic solvents is not required.
한편, 기존의 PPS는 금속과의 접착 시 사출 유동 선단에서 발생되는 많은 양의 아웃 가스(out gas; 저분자량 올리고머)로 인하여 금속 표면의 미세한 공극들을 채우지 못하고, 그로 인하여 금속 접착성이 저하되는 문제가 발생하였다. 이에, PPS와 금속의 접착성을 향상시키기 위한 대안으로, 극성기를 함유한 폴리올레핀 및 상용화제를 PPS와 컴파운딩하여 제조한 수지 조성물이 제안된 바 있으나, 이러한 상용화제나 극성기를 함유하는 폴리올레핀과 같은 올리고머의 사용은 PPS의 기계적 물성을 저하시키거나 열적 특성을 약화시키는 문제점이 있었다.On the other hand, the conventional PPS is unable to fill the fine pores of the metal surface due to the large amount of out gas (low molecular weight oligomer) generated in the injection flow front when bonding with the metal, thereby deteriorating the metal adhesion Occurred. Therefore, as an alternative to improve the adhesion between the PPS and the metal, a resin composition prepared by compounding a polyolefin containing a polar group and a compatibilizer with PPS has been proposed, but an oligomer such as a polyolefin containing such a compatibilizer or a polar group has been proposed. The use of has a problem of lowering the mechanical properties of PPS or weakening the thermal properties.
따라서, 기존의 금속 접착 플라스틱의 근본적인 문제인 유동 선단에서 발생되는 아웃 가스의 양을 줄이면서, 염소와 같은 부산물의 함량이 적고 금속과의 접착성이 우수한 PAS 조성물의 개발이 요구되는 실정이다.Therefore, while reducing the amount of outgas generated in the flow front, which is a fundamental problem of the conventional metal-bonded plastic, there is a need for the development of a PAS composition having a low content of by-products such as chlorine and excellent adhesion to metal.
이에, 본 발명의 목적은 유동 선단에서 발생되는 아웃 가스의 양이 적고, 백색도, 내산성 및 금속과의 접착성이 우수한 수지 조성물을 제공하는 것이다.Accordingly, an object of the present invention is to provide a resin composition having a small amount of outgas generated at the flow front and excellent in whiteness, acid resistance and adhesion to metal.
또한, 본 발명의 다른 목적은 상기 수지 조성물을 성형하여 제조된 성형품을 제공하는 것이다.Another object of the present invention is to provide a molded article produced by molding the resin composition.
상기 목적을 달성하기 위해 본 발명은, 폴리아릴렌 설파이드; 및 하기 화학식 1로 표시되는 반복단위를 포함하는 폴리사이클로헥실렌디메틸렌 테레프탈레이트(polycyclohexylenedimethylene terephthalate; PCT)를 포함하고, 아웃가스 함량이 300 ppm 이하인 수지 조성물을 제공한다:The present invention to achieve the above object, Polyarylene sulfide; And a polycyclohexylenedimethylene terephthalate (PCT) comprising a repeating unit represented by the following Chemical Formula 1, and provides a resin composition having an outgas content of 300 ppm or less:
Figure PCTKR2017000612-appb-C000001
Figure PCTKR2017000612-appb-C000001
또한, 본 발명은 상술한 바와 같은 수지 조성물을 성형하여 제조된 성형품을 제공한다.The present invention also provides a molded article produced by molding the resin composition as described above.
본 발명에 따른 수지 조성물은, PAS 특유의 우수한 기계적 및 열적 물성을 저하시키지 않으면서 낮은 아웃 가스 함량을 가져 우수한 금속 접착 성능을 나타낸다. 이로 인해, 상기 수지 조성물은 사출 인서트 성형으로 일체화되는 전자 부품에서부터 자동차 부품에 이르기까지 다양한 분야에서 다양한 용도로 적용할 수 있다. 또한, 상기 수지 조성물은 염 형태의 부산물을 소량으로 포함하여 전자 제품의 성능을 저하시키지 않으므로 휴대폰이나 노트북 등의 내장 소재로 유용하게 사용될 수 있다. 나아가, 상기 수지 조성물은 산처리 후에도 높은 백색도 구현이 가능하여 내장재뿐만 아니라 외장재의 소재로도 활용할 수 있다.The resin composition according to the present invention has a low out gas content without degrading the excellent mechanical and thermal properties peculiar to PAS and thus exhibits excellent metal adhesion performance. For this reason, the said resin composition can be applied to various uses in various fields from the electronic component integrated with injection insert molding to an automotive component. In addition, the resin composition may contain a small amount of by-products in a salt form, and thus may not be deteriorated in the performance of electronic products. Further, the resin composition can be implemented as a high whiteness even after the acid treatment can be utilized as a material of the exterior material as well as interior materials.
도 1은 본 발명의 수지 조성물을 이용하여 금속접착강도 측정용 시편을 제조하는 일부 과정을 도시화한 것이다.Figure 1 illustrates a part of the process for producing a test piece for measuring the metal adhesive strength using the resin composition of the present invention.
본 발명은 폴리아릴렌 설파이드; 및 하기 화학식 1로 표시되는 반복단위를 포함하는 폴리사이클로헥실렌디메틸렌테레프탈레이트를 포함하는 수지 조성물을 제공한다:The present invention is polyarylene sulfide; And it provides a resin composition comprising a polycyclohexylene dimethylene terephthalate comprising a repeating unit represented by the formula (1):
[화학식 1][Formula 1]
Figure PCTKR2017000612-appb-I000001
Figure PCTKR2017000612-appb-I000001
본 발명의 수지 조성물은 300 ppm 이하의 낮은 아웃 가스 함량을 가져 우수한 금속 접착 성능을 나타낸다. 구체적으로, 상기 수지 조성물은 150 내지 300 ppm의 아웃가스를 함유할 수 있다.The resin composition of the present invention has a low out gas content of 300 ppm or less and shows excellent metal adhesion performance. Specifically, the resin composition may contain 150 to 300 ppm of outgas.
상기 수지 조성물은 염소의 함량이 300 ppm 이하로서, 소량의 염 형태의 부산물을 포함하여 전자 제품의 성능을 저하시키지 않는다. 구체적으로, 상기 수지 조성물의 염소 함량은 200 ppm 이하, 100 ppm 이하이며, 예를 들어 0 초과 내지 100 ppm이고, 더욱 구체적으로 50 ppm 이하일 수 있다. The resin composition has a chlorine content of 300 ppm or less and does not reduce the performance of the electronic product by including a small amount of by-products in the form of salt. Specifically, the chlorine content of the resin composition is 200 ppm or less, 100 ppm or less, for example, more than 0 to 100 ppm, more specifically 50 ppm or less.
상기 수지 조성물은 ISO 527에 따라 측정한 인장강도 값이 80 ㎫ 이상, 구체적으로 80 내지 150 ㎫일 수 있다.The resin composition may have a tensile strength value of 80 MPa or more, specifically 80 to 150 MPa, measured according to ISO 527.
상기 수지 조성물은 ASTM D 3163에 따라 측정한 금속접착강도 값이 60 ㎫ 이상, 구체적으로 60 내지 80 ㎫일 수 있다.The resin composition may have a metal adhesive strength value of 60 MPa or more, specifically 60 to 80 MPa, measured according to ASTM D 3163.
또한, 상기 수지 조성물은 D65 광원의 경면반사광포함(specular component included, SCI) 모드에 따라 측정한 L 값이 89 이상, 구체적으로 90 내지 93일 수 있다. 상기 L값이 높을수록 백색도가 우수하다.In addition, the resin composition may have an L value of 89 or more, specifically 90 to 93, measured according to a specular component included (SCI) mode of the D65 light source. The higher the L value, the better the whiteness.
상기 수지 조성물은 양극산화처리(anodizing) 후 ASTM D 3163에 따라 측정한 금속접착강도값이 55 ㎫ 이상, 구체적으로 55 내지 80 ㎫일 수 있다.The resin composition may have a metal adhesive strength value of 55 MPa or more, specifically 55 to 80 MPa, measured according to ASTM D 3163 after anodizing.
상기 수지 조성물은 산을 이용한 화학적 방법으로 양극산화처리(anodizing) 후 D65 광원의 SCI 모드에 따라 측정한 L값이 88 이상, 구체적으로 88 내지 93일 수 있다.The resin composition may have an L value of 88 or more, specifically 88 to 93, measured according to the SCI mode of the D65 light source after anodizing by an acidic chemical method.
이하, 본 발명의 구성성분을 구체적으로 설명한다.Hereinafter, the component of this invention is demonstrated concretely.
본 발명의 수지 조성물은 폴리아릴렌 설파이드를 포함한다.The resin composition of this invention contains polyarylene sulfide.
상기 폴리아릴렌 설파이드는 주쇄에 결합된 요오드 및 유리 요오드를 포함하며, 구체적으로, 상기 주쇄에 결합된 요오드 및 유리 요오드 함량은 10 내지 10,000 ppm일 수 있다. 상기 주쇄에 결합된 요오드 및 유리 요오드 함량은 하기 실시예의 기재와 같이, 폴리아릴렌 설파이드 시료를 고온에서 열처리한 후, 이온크로마토그래피를 이용해 정량하는 방법으로 측정할 수 있다. 상기 유리 요오드는 디요오드 방향족 화합물과 황 원소의 중합 과정에서 발생하며, 최종 형성된 폴리아릴렌 설파이드와 화학적으로 분리된 상태로 잔류하는 요오드 분자, 요오드 이온 또는 요오드 라디칼 등을 총칭하는 것을 의미한다.The polyarylene sulfide includes iodine and free iodine bonded to the main chain, and specifically, the content of iodine and free iodine bonded to the main chain may be 10 to 10,000 ppm. The iodine and free iodine content bound to the main chain may be measured by quantitatively using ion chromatography after heat-treating a polyarylene sulfide sample at high temperature as described in the following Examples. The free iodine occurs during the polymerization of the diiodine aromatic compound and the elemental sulfur, and refers to the iodine molecules, iodine ions, or iodine radicals, etc., which remain in a chemically separated state from the polyarylene sulfide finally formed.
상기 폴리아릴렌 설파이드는 디요오드 방향족 화합물과 황 원소를 포함하는 반응물을 용융 중합하여 제조할 수 있다. 상기 중합반응에 사용 가능한 디요오드 방향족 화합물로는 디요오도벤젠(diiodobenzene; DIB), 디요오도나프탈렌(diiodonaphthalene), 디요오도비페닐(diiodobiphenyl), 디요오도비스페놀(diiodobisphenol), 및 디요오도벤조페논(diiodobenzophenone)으로 이루어진 군에서 선택되는 1종 이상을 들 수 있지만, 이에 한정되지 않는다. 또한, 상술한 디요오드 방향족 화합물들에 알킬 원자단(alkyl group)이나 술폰 원자단(sulfone group) 등이 치환기로 결합되어 있거나, 방향족기에 산소나 질소 등의 원자가 함유된 형태의 디요오드 방향족 화합물도 사용될 수 있다. 나아가, 상기 디요오드 방향족 화합물은 요오드 원자가 붙은 위치에 따라 여러 가지 디요오드 화합물의 이성질체(isomer)가 있는데, 이 중에서도 파라-디요오도벤젠(pDIB), 2,6-디요오도나프탈렌, 또는 p,p'-디요오도비페닐처럼 파라 위치에 요오드가 결합된 화합물이 보다 적합하다. The polyarylene sulfide may be prepared by melt polymerization of a reactant containing a diiodine aromatic compound and elemental sulfur. Diiodine aromatic compounds that can be used for the polymerization reaction include diododobenzene (DIB), diiodonaphthalene, diiodobiphenyl, diiodobisphenol, and diiodophenol One or more selected from the group consisting of benzophenone (diiodobenzophenone), but is not limited thereto. In addition, an alkyl group or a sulfone group may be bonded to the above-mentioned diiodine aromatic compounds with a substituent, or a diiodine aromatic compound in which atoms such as oxygen or nitrogen are contained in the aromatic group may also be used. have. Furthermore, the diiodine aromatic compound has isomers of various diiodine compounds depending on the position of the iodine atom, among them, para-diiodobenzene (pDIB), 2,6-diiodonaphthalene, or p More suitable are compounds in which iodine is bonded in the para position, such as p'-diiodobiphenyl.
상기 디요오드 방향족 화합물과 반응하는 황 원소의 형태에는 별다른 제한이 없다. 보통 황 원소는 상온에서 원자 8개가 연결된 고리 형태(cyclooctasulfur; S8)로 존재하는데, 이러한 형태가 아니더라도 상업적으로 사용 가능한 고체 또는 액체 상태의 황이라면 별다른 한정 없이 모두 사용할 수 있다. There is no restriction | limiting in particular in the form of elemental sulfur which reacts with the said diiodine aromatic compound. Usually, elemental sulfur is present in the form of a ring (cyclooctasulfur; S 8 ) having 8 atoms connected at room temperature. If it is not in this form, any commercially available solid or liquid sulfur may be used without particular limitation.
또한, 상기 디요오드 방향족 화합물과 반응물의 혼합물은 중합개시제, 안정제, 또는 이들의 혼합물을 추가로 포함할 수 있다. 상기 중합개시제는 1,3-디요오도-4-니트로벤젠, 머캅토벤조티아졸, 2,2'-디티오벤조티아졸, 사이클로헥실벤조티아졸 술펜아미드, 및 부틸벤조티아졸 술펜아미드로 이루어진 군에서 선택되는 1종 이상을 포함할 수 있으나, 상술한 예에 한정되지는 않는다.In addition, the mixture of the diiodine aromatic compound and the reactant may further include a polymerization initiator, a stabilizer, or a mixture thereof. The polymerization initiator is 1,3-diiodo-4-nitrobenzene, mercaptobenzothiazole, 2,2'-dithiobenzothiazole, cyclohexylbenzothiazole sulfenamide, and butylbenzothiazole sulfenamide. It may include one or more selected from the group consisting of, but is not limited to the above examples.
상기 안정제는 통상 수지의 중합반응에 사용되는 안정제이면, 특별히 한정되지 않는다.The stabilizer is not particularly limited as long as it is a stabilizer usually used for polymerization of the resin.
한편, 상기 혼합물의 용융중합 도중, 중합중지제를 첨가할 수 있다. 상기 중합 중지제는 중합되는 고분자에 포함되는 요오드 그룹을 제거하여 중합을 중지 시킬 수 있는 화합물이면 특별히 한정되지 않는다. 구체적으로, 디페닐 설파이드(diphenyl sulfide), 디페닐 에테르(diphenyl ether), 디페닐(diphenyl), 벤조페논(benzophenone), 디벤조티아졸 디설파이드(dibenzothiazole disulfide), 모노요오도아릴 화합물(monoiodoaryl compound), 벤조티아졸(benzothiazole)류, 벤조티아졸 술펜아미드(benzothiazole sulfenamide)류, 티우람(thiuram)류 및 디티오카바메이트(dithiocarbamate)류로 이루어진 군에서 선택되는 1종 이상일 수 있다. 보다 구체적으로, 상기 중합중지제는 요오도비페닐(iodobiphenyl), 요오도페놀(iodophenol), 요오도아닐린(iodoaniline), 요오도벤조페논(iodobenzophenone), 2-메르캅토벤조티아졸(2-mercaptobenzothiazole), 2,2'-디티오비스벤조티아졸(2,2'-dithiobisbenzothiazole), N-시클로헥실벤조티아졸-2-술펜아미드(N-cyclohexylbenzothiazole-2-sulfenamide), 2-모르폴리노티오벤조티아졸(2-morpholinothiobenzothiazole), N,N-디시클로헥실벤조티아졸-2-술펜아미드(N,N-dicyclohexylbenzothiazole-2-sulfenamide), 테트라메틸티우람 모노설파이드(tetramethylthiuram monosulfide), 테트라메틸티우람 디설파이드(tetramethylthiuram disulfide), 아연 디메틸디티오카바메이트(Zinc dimethyldithiocarbamate), 아연 디에틸디티오카바메이트(Zinc diethyldithiocarbamate) 및 디페닐 디설파이드(diphenyl disulfide)로 이루어진 군에서 선택되는 1종 이상일 수 있다.Meanwhile, during the melt polymerization of the mixture, a polymerization terminator may be added. The polymerization inhibitor is not particularly limited as long as it is a compound capable of stopping the polymerization by removing the iodine group contained in the polymer to be polymerized. Specifically, diphenyl sulfide, diphenyl ether, diphenyl, diphenyl, benzophenone, dibenzothiazole disulfide, and monoiodoaryl compound , Benzothiazoles, benzothiazole sulfenamides, thiurams, and dithiocarbamates may be one or more selected from the group consisting of. More specifically, the polymerization terminator is iodobiphenyl (iodobiphenyl), iodophenol (iodophenol), iodoaniline (iodoaniline), iodobenzophenone (iodobenzophenone), 2-mercaptobenzothiazole (2-mercaptobenzothiazole) , 2,2'-dithiobisbenzothiazole, N-cyclohexylbenzothiazole-2-sulfenamide, 2-morpholinothiobenzothia 2-morpholinothiobenzothiazole, N, N-dicyclohexylbenzothiazole-2-sulfenamide, tetramethylthiuram monosulfide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide (tetramethylthiuram disulfide), zinc dimethyldithiocarbamate (Zinc dimethyldithiocarbamate), zinc diethyldithiocarbamate (Zinc diethyldithiocarbamate) and may be one or more selected from the group consisting of diphenyl disulfide (diphenyl disulfide).
상기 중합중지제의 투여 시점은 중합시키고자 하는 폴리아릴렌 설파이드의 분자량을 고려하여 결정할 수 있다. 예를 들어, 초기 반응물 내에 포함된 디요오드 방향족 화합물을 기준으로 약 70 내지 100 중량%가 반응되어 소진된 시점에서 투여할 수 있다.The timing of administration of the polymerization terminator may be determined in consideration of the molecular weight of the polyarylene sulfide to be polymerized. For example, about 70 to 100% by weight based on the diiodine aromatic compound included in the initial reactant may be administered when the reaction is exhausted.
또한, 상술한 바와 같은 용융중합은 디요오드 방향족 화합물과 황 원소를 포함하는 반응물의 중합이 개시될 수 있는 조건이면 특별히 한정되지 않는다. 예를 들어, 상기 용융중합은 승온 감압 조건에서 진행될 수 있는데, 이 경우, 180 내지 250℃ 및 50 내지 450 torr의 초기 반응조건에서 온도 상승 및 압력 강하를 수행하여 최종 반응조건인 270 내지 350℃ 및 0.001 내지 20 torr로 변화시키며, 약 1 내지 30 시간 동안 진행할 수 있다. 보다 구체적인 예로서, 최종 반응조건을 온도 약 280 내지 300℃ 및 압력 약 0.1 내지 1 torr로 하여 중합반응을 진행할 수 있다.In addition, melt polymerization as mentioned above is not specifically limited as long as it can start the superposition | polymerization of the reaction material containing a diiodine aromatic compound and elemental sulfur. For example, the melt polymerization may be performed at elevated temperature and reduced pressure conditions, in which case, the final reaction conditions of 270 to 350 ° C. and temperature rise and pressure drop are performed at initial reaction conditions of 180 to 250 ° C. and 50 to 450 torr. The amount can be changed to 0.001 to 20 torr, and can proceed for about 1 to 30 hours. As a more specific example, the polymerization reaction may be carried out at a final reaction condition of about 280 to 300 ° C. and about 0.1 to 1 torr of pressure.
한편, 폴리아릴렌 설파이드의 제조 방법은 상기 용융중합 전에, 디요오드 방향족 화합물과 황 원소를 포함하는 반응물을 용융 혼합하는 단계를 추가로 포함할 수 있다. 이와 같은 용융 혼합은 상기 혼합물이 용융 혼합될 수 있는 조건이면 특별히 한정되지 않는다. 예를 들어, 130 내지 200℃, 혹은 160 내지 190℃의 온도에서 진행할 수 있다. 상술한 바와 같이 용융중합 전에 용융 혼합 단계를 진행하는 경우, 추후 행해지는 용융중합을 보다 용이하게 진행할 수 있다.Meanwhile, the method for preparing polyarylene sulfide may further include melt mixing a reactant including a diiodine aromatic compound and elemental sulfur before the melt polymerization. Such melt mixing is not particularly limited as long as the mixture can be melt mixed. For example, it may proceed at a temperature of 130 to 200 ℃, or 160 to 190 ℃. As described above, when the melt mixing step is performed before the melt polymerization, subsequent melt polymerization can be performed more easily.
본 발명의 다른 일구현예에 따른 폴리아릴렌 설파이드의 제조 방법에 있어서, 상기 용융중합은 니트로벤젠계 촉매의 존재 하에서 진행될 수 있다. 또한, 상술한 바와 같이 용융중합반응 전에 용융 혼합 단계를 거치는 경우, 상기 니트로벤젠계 촉매는 용융 혼합 단계에서 추가될 수 있다. 예를 들어, 니트로벤젠계 촉매는 1,3-디요오도-4-니트로벤젠, 또는 1-요오도-4-니트로벤젠 등을 들 수 있으나, 이에 한정되지 않는다.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 catalyst. In addition, as described above, when the melt mixing step is performed before the melt polymerization reaction, the nitrobenzene-based catalyst may be added in the melt mixing step. For example, the nitrobenzene-based catalyst may include 1,3-diiodo-4-nitrobenzene, or 1-iodo-4-nitrobenzene, but is not limited thereto.
상술한 바와 같이 제조된 폴리아릴렌 설파이드는 기존의 제조 공정과는 다르게 염 형태의 부산물을 거의 생산하지 않는다. 예를 들어, 본 발명의 폴리아릴렌 설파이드는 염소 함량이 300 ppm 이하, 구체적으로 200 ppm 이하, 더욱 구체적으로 100 ppm 이하일 수 있다.Polyarylene sulfides prepared as described above produce little by-products in salt form, unlike conventional manufacturing processes. For example, the polyarylene sulfide of the present invention may have a chlorine content of 300 ppm or less, specifically 200 ppm or less, more specifically 100 ppm or less.
상기 폴리아릴렌 설파이드는 융점이 약 265 내지 290℃, 약 270 내지 285℃, 또는 약 275 내지 283℃일 수 있다. 또한, 수평균분자량이 약 5,000 내지 50,000, 약 8,000 내지 40,000, 또는 약 10,000 내지 30,000일 수 있다. 나아가, 상기 폴리아릴렌 설파이드는 수평균분자량에 대한 중량평균분자량으로 정의되는 분산도가 약 2.0 내지 4.5, 약 2.0 내지 4.0, 또는 약 2.0 내지 3.5일 수 있다.The polyarylene sulfide may have a melting point of about 265 to 290 ° C, about 270 to 285 ° C, or about 275 to 283 ° C. In addition, the number average molecular weight may be 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 dispersion degree defined as a weight average molecular weight with respect to the number average molecular weight, about 2.0 to 4.5, about 2.0 to 4.0, or about 2.0 to 3.5.
상기 폴리아릴렌 설파이드는 회전 원판 점도계로 300℃에서 측정한 용융 점도가 약 10 내지 50,000 poise, 약 100 내지 20,000 poise, 또는 약 300 내지 10,000 poise일 수 있다.The polyarylene sulfide may have a melt viscosity of about 10 to 50,000 poise, about 100 to 20,000 poise, or about 300 to 10,000 poise, measured at 300 ° C. with a rotating disc viscometer.
한편, 본 발명의 수지 조성물은 폴리사이클로헥실렌디메틸렌 테레프탈레이트를 포함한다. 상기 폴리사이클로헥실렌디메틸렌테레프탈레이트는 하기 화학식 1로 표시되는 반복단위를 포함한다. On the other hand, the resin composition of this invention contains polycyclohexylenedimethylene terephthalate. The polycyclohexylenedimethylene terephthalate includes a repeating unit represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2017000612-appb-I000002
Figure PCTKR2017000612-appb-I000002
상기 화학식 1로 표시되는 반복단위를 포함하는 PCT는 중량평균분자량이 10,000 내지 200,000, 또는 30,000 내지 70,000일 수 있으며, 고유 점도(IV)가 0.1 내지 1 ㎗/g, 또는 0.5 내지 0.8 ㎗/g일 수 있다. 또한, 상기 PCT는 분광측색계를 이용하여 D65 광원의 경면반사광포함 모드로 측정한 L값이 80 이상, 구체적으로 85 이상일 수 있으며, b값이 10 이하, 구체적으로 6 이하일 수 있다.PCT including a repeating unit represented by Formula 1 may have a weight average molecular weight of 10,000 to 200,000, or 30,000 to 70,000, intrinsic viscosity (IV) of 0.1 to 1 dl / g, or 0.5 to 0.8 dl / g Can be. In addition, the PCT may have an L value of 80 or more, specifically 85 or more, and a b value of 10 or less, specifically 6 or less, measured in a specular colorimeter using a specular colorimeter with a specular spectrophotometer.
상기 PCT는 디올 화합물과 디카르복실산의 혼합물에 게르마늄 화합물을 포함하는 촉매를 투입하고 교반하며 에스테르화 반응 및 중축합 반응을 행하는 단계를 포함하는 통상적인 제조방법으로 제조될 수 있다.The PCT may be prepared by a conventional manufacturing method including adding a catalyst containing a germanium compound to a mixture of a diol compound and a dicarboxylic acid, stirring the same, and performing an esterification reaction and a polycondensation reaction.
상기 수지 조성물은 PAS 100 중량부에 대하여 0.5 내지 50 중량부, 1 내지 40 중량부, 또는 3 내지 30 중량부의 PCT를 포함할 수 있다. 상기 PCT가 PAS 100 중량부에 대하여 0.5 중량부 이상으로 포함되면 금속 접착력 및 백색도가 우수하고, 50 중량부 이하로 포함되면 수지 조성물의 기계적 강도 저하의 문제가 발생하지 않는다.The resin composition may include 0.5 to 50 parts by weight, 1 to 40 parts by weight, or 3 to 30 parts by weight of PCT based on 100 parts by weight of PAS. When the PCT is included in an amount of 0.5 parts by weight or more based on 100 parts by weight of PAS, the metal adhesion and whiteness are excellent.
본 발명의 일구현예에 따르면, 수지 조성물이 PCT를 포함함으로써 기존의 PAS 수지 조성물이 가질 수 없었던 우수한 백색도 및 금속 접착능을 나타낼 뿐만 아니라, 양극산화반응(anodizing) 후에도 백색도 및 금속 접착능 유지율이 높게 나타났다.According to one embodiment of the present invention, since the resin composition contains PCT, the resin composition exhibits excellent whiteness and metal adhesion that the conventional PAS resin composition could not have, and also maintains the whiteness and metal adhesion after anodizing. High.
또한, 본 발명의 수지 조성물은 페녹시 수지, 엘라스토머, 충진재, 충격 흡수제, 접착력 향상제, 안정제, 안료, 가소제, 활제 및 핵제로 이루어진 군으로부터 선택되는 1종 이상의 성분을 더 포함할 수 있다.In addition, the resin composition of the present invention may further include one or more components selected from the group consisting of phenoxy resins, elastomers, fillers, shock absorbers, adhesion enhancers, stabilizers, pigments, plasticizers, lubricants and nucleating agents.
상기 수지 조성물은 페녹시 수지를 더 포함할 수 있으며, 페녹시 수지를 더 포함함으로써 수지 조성물의 금속 접착능을 향상시킬 수 있다. 구체적으로, 상기 페녹시 수지는 중량평균분자량이 10,000 내지 250,000이고, 유리 전이 온도가 50 내지 130℃일 수 있다. 보다 구체적으로, 상기 페녹시 수지는 하기 화학식 2로 표시될 수 있다. 더욱 구체적으로, 상기 페녹시 수지는 비스페놀 A(bisphenol A, BPA)를 포함할 수 있으며, 중량평균분자량이 20,000 내지 220,000이고, 유리 전이 온도가 60 내지 120℃일 수 있다.The resin composition may further include a phenoxy resin, and may further include a phenoxy resin to improve metal adhesion of the resin composition. Specifically, 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 specifically, the phenoxy resin may be represented by the following formula (2). More specifically, the phenoxy resin may include bisphenol A (bisphenol A, BPA), the weight average molecular weight is 20,000 to 220,000, the glass transition temperature may be 60 to 120 ℃.
Figure PCTKR2017000612-appb-C000002
Figure PCTKR2017000612-appb-C000002
상기 화학식 2에서, n은 100 내지 900의 정수이다. 구체적으로, 상기 n은 100 내지 700의 정수, 100 내지 500의 정수, 100 내지 300의 정수, 200 내지 300의 정수 또는 300 내지 500의 정수일 수 있다.In Formula 2, n is an integer of 100 to 900. Specifically, 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.
상기 페녹시 수지는 말단이 수산기 및/또는 카르복실기로 치환될 수 있다.The phenoxy resin may be substituted at the terminal with a hydroxyl group and / or a carboxyl group.
상기 수지 조성물은 PAS 100 중량부에 대하여 1 내지 75 중량부의 페녹시 수지를 포함할 수 있다. 구체적으로, 상기 페녹시 수지는 PAS 100 중량부에 대하여 3 내지 15 중량부의 양으로 첨가될 수 있다.The resin composition may include 1 to 75 parts by weight of phenoxy resin based on 100 parts by weight of PAS. Specifically, the phenoxy resin may be added in an amount of 3 to 15 parts by weight based on 100 parts by weight of PAS.
본 발명의 수지 조성물에 엘라스토머를 추가로 포함시킴으로써 수지 조성물에 인성(toughness)을 부여하여 금속 접착 이후에 온도 변화에 따라 수지와 금속의 계면 분리를 방지하는 효과를 나타낼 수 있다. 상기 엘라스토머는 예를 들면, 폴리염화비닐계 엘라스토머, 폴리올레핀계 엘라스토머, 폴리우레탄계 엘라스토머, 폴리에스테르계 엘라스토머, 폴리아미드계 엘라스토머, 폴리부타디엔계 엘라스토머, 및 글리시딜 메타 아크릴레이트와 메틸 아크릴 에스테르, 에틸렌의 삼원 공중합체 엘라스토머로 이루어진 군으로부터 선택되는 1종 이상의 열가소성 엘라스토머일 수 있으며, 구체적으로, 글리시딜 메타 아크릴레이트와 메틸 아크릴 에스테르, 에틸렌의 삼원 공중합체 엘라스토머일 수 있다.By further including an elastomer in the resin composition of the present invention, it is possible to impart toughness to the resin composition to prevent the interface separation between the resin and the metal according to the temperature change after the metal adhesion. The elastomer may be, for example, a polyvinyl chloride elastomer, a polyolefin elastomer, a polyurethane elastomer, a polyester elastomer, a polyamide elastomer, a polybutadiene elastomer, a glycidyl methacrylate, methyl acrylic ester, or ethylene. It may be one or more thermoplastic elastomers selected from the group consisting of terpolymer copolymers, specifically, terpolymer copolymer elastomers of glycidyl methacrylate, methyl acrylic ester and ethylene.
상기 수지 조성물은 PAS 100 중량부에 대하여 1 내지 75 중량부, 구체적으로 3 내지 35 중량부의 엘라스토머를 포함할 수 있다.The resin composition may include 1 to 75 parts by weight, specifically 3 to 35 parts by weight of elastomer, based on 100 parts by weight of PAS.
상기 충진재는 예를 들면, 유리 섬유, 탄소 섬유, 붕소 섬유, 유리 비드, 유리 플레이크, 활석, 탈크 및 탄산칼슘으로 이루어진 군으로부터 선택된 1종 이상일 수 있으며, 구체적으로, 유리 섬유일 수 있다. 또한, 상기 유리 섬유는 에폭시 실란, 아미노 실란 및 이의 조합으로 이루어진 군으로부터 선택된 실란으로 처리된 유리 섬유일 수 있으며, 구체적으로 에폭시 실란으로 처리된 유리 섬유일 수 있다. The filler may be, for example, one or more selected from the group consisting of glass fibers, carbon fibers, boron fibers, glass beads, glass flakes, talc, talc and calcium carbonate, specifically, may be glass fibers. In addition, the glass fiber may be a glass fiber treated with a silane selected from the group consisting of epoxy silane, amino silane and combinations thereof, and specifically, may be glass fiber treated with epoxy silane.
상기 충진재는 파우더나 플레이크 형태일 수 있으나, 이에 특별히 제한되지 않는다. The filler may be in the form of powder or flake, but is not particularly limited thereto.
상기 수지 조성물은 PAS 100 중량부에 대하여 5 내지 250 중량부, 구체적으로 10 내지 150 중량부의 충진재를 포함할 수 있다.The resin composition may include 5 to 250 parts by weight, specifically 10 to 150 parts by weight of filler, based on 100 parts by weight of PAS.
상기 안료는 당업계에 공지된 통상적인 각종 유기 또는 무기 안료일 수 있으며, 예를 들어 황화 아연(ZnS), 산화 아연(ZnO), 이산화 티타늄(TiO2) 및 이의 조합으로 이루어진 군으로부터 선택될 수 있다. 구체적으로, 상기 안료는 황화 아연(ZnS)일 수 있다. The pigment may be any of a variety of conventional organic or inorganic pigments known in the art and may be selected, for example, from the group consisting of zinc sulfide (ZnS), zinc oxide (ZnO), titanium dioxide (TiO 2 ) and combinations thereof. have. Specifically, the pigment may be zinc sulfide (ZnS).
상기 안료는 PAS 100 중량부에 대하여 0.1 내지 50 중량부, 구체적으로 0.3 내지 25 중량부의 양으로 첨가될 수 있다.The pigment may be added in an amount of 0.1 to 50 parts by weight, specifically 0.3 to 25 parts by weight, based on 100 parts by weight of PAS.
상기 안정제는 예를 들면, 산화 방지제, 광 안정제 및 이의 조합 등을 들 수 있다. 또한, 상기 안정제는 PAS 100 중량부에 대하여 0.1 내지 10 중량부의 양으로 첨가될 수 있다.Examples of the stabilizer include antioxidants, light stabilizers, combinations thereof, and the like. In addition, the stabilizer may be added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of PAS.
상기 산화 방지제는 수지 조성물의 높은 내열성 및 열안정성을 지지하는 역할을 할 수 있는 것이라면 특별히 제한되지 않으며, 예를 들면, 페놀계, 아민계, 유황계 또는 인계 산화 방지제를 들 수 있다. 상기 페놀계 산화 방지제는 예를 들면, 힌다드 페놀계 화합물일 수 있고, 구체적인 예로는 테트라키스[메틸렌-3-(3,5-디-터트-부틸-4-하이드록시페닐)프로피오네이트]메탄, 티오디에틸렌 비스[3-(3,5-디-터트-부틸-4-하이드록시페닐)프로피오네이트], N,N'-헥산-1,6-디일비스[3-(3,5- 디-터트-부틸-4-하이드록시페닐)프로피온아미드] 등을 들 수 있다. 상기 인계 산화 방지제는 예를 들면, 트리스(2,4-디-터트-부틸페닐)포스페이트, O,O'-디옥타데실펜타에리트리톨 비스(포스파이트), 비스(2.4-디-터트-부틸페닐)펜타에리트리톨 디포스파이트, 3,9-비스(2,4-디-터트-부틸페녹시)-2,4,8,10-테트라옥사-3,9-디포스파스피로[5.5]운데칸 등을 들 수 있다. The antioxidant is not particularly limited as long as it can play a role of supporting high heat resistance and thermal stability of the resin composition, and examples thereof include a phenol-based, amine-based, sulfur-based or phosphorus-based antioxidant. The phenolic antioxidant may be, for example, a hindered phenolic compound, and specific examples thereof may be tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. Methane, thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide]. The phosphorus antioxidants include, for example, 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-tetraoxa-3,9-diphosphaspiro [5.5] undecane Etc. can be mentioned.
상기 광 안정제는 자외선 흡수 및 차단 역할을 할 수 있는 것이라면 특별히 제한하지 않으며, 예를 들면 벤조페논(benzophenone)계 화합물, 살리실레이트(salicylate)계 화합물, 벤조트리아졸(benzotriazole)계 화합물, 아크릴로니트릴(acrylonitrile)계 화합물, 그 밖의 공명구조 화합물 등의 자외선 흡수 효과가 있는 화합물, 힌더드 아민(hindered amine)계 화합물, 힌더드 페놀(hindered phenol)계 화합물 등의 라디칼(radical) 포착 능력이 있는 화합물, 또는 이의 조합 등을 사용할 수 있다. 또한, 자외선 흡수 효과가 있는 화합물과 라디칼(radical) 포착 능력이 있는 화합물을 함께 사용하면 보다 높은 자외선 흡수 및 차단 효과를 나타낼 수 있다.The light stabilizer is not particularly limited as long as it can act as a UV absorbing and blocking, for example, benzophenone compound, salicylate compound, benzotriazole compound, acryl UV-absorbing compounds such as nitrile compounds, other resonance structure compounds, and the like, and have a radical trapping ability such as hindered amine compounds and hindered phenol compounds. Compounds, combinations thereof, and the like can be used. In addition, when a compound having a UV absorbing effect and a compound having a radical trapping ability are used together, a higher UV absorbing and blocking effect can be obtained.
성형성을 향상시키기 위하여 상기 수지 조성물은 활제를 더 포함할 수 있으며, 특히 탄화수소계의 활제를 사용하여 수지와 금형의 금속과의 마찰방지, 금형에서의 용이한 탈착성(이형성)을 부여할 수 있다. 상기 탄화수소계 활제는 특별히 제한하지 않으나, 예를 들면 파라핀 왁스, 폴리에스테르(PE) 왁스, 폴리프로필렌(PP) 왁스, 산화 폴리에스테르 왁스 및 이의 조합으로 이루어진 군으로부터 선택될 수 있다. 또한, 상기 활제는 수지 조성물에 PAS 100 중량부에 대하여 0.1 내지 10 중량부, 구체적으로 0.5 내지 5 중량부의 양으로 첨가될 수 있다.In order to improve moldability, the resin composition may further include a lubricant, and in particular, a hydrocarbon-based lubricant may be used to prevent friction between the resin and the metal of the mold and to provide easy detachability (releasability) in the mold. have. The hydrocarbon-based lubricant is not particularly limited, but may be selected from the group consisting of, for example, paraffin wax, polyester (PE) wax, polypropylene (PP) wax, oxidized polyester wax, and combinations thereof. In addition, the lubricant may be added to the resin composition in an amount of 0.1 to 10 parts by weight, specifically 0.5 to 5 parts by weight based on 100 parts by weight of PAS.
한편, 본 발명은 상기 수지 조성물로부터 제조된 성형품을 제공할 수 있다.On the other hand, this invention can provide the molded article manufactured from the said resin composition.
상술한 바와 같은 수지 조성물을 이축 압출 등 당업계에 공지된 방법으로 성형하여 다양한 용도에 적용 가능한, 우수한 금속 접착성, 백색도 및 내산성을 갖는 성형품으로 제조할 수 있다.The resin composition as described above may be molded by a method known in the art such as biaxial extrusion to produce a molded article having excellent metal adhesion, whiteness and acid resistance, which can be applied to various applications.
상기 성형품은 필름, 시트, 또는 섬유 등의 다양한 형태일 수 있으며, 사출 성형품, 압출 성형품, 또는 블로우 성형품일 수 있다. 사출 성형하는 경우의 금형 온도는, 결정화의 관점에서 130℃ 이상일 수 있다. 또한, 상기 성형품이 필름 또는 시트 형태인 경우, 미연신, 1축 연신, 2축 연신 등의 방법을 이용하여 각종 필름 또는 시트로 제조할 수 있다. 상기 성형품이 섬유인 경우, 미연신사, 연신사, 또는 초연신사 등 각종 섬유일 수 있고, 직물, 편물, 부직포(스펀본드, 멜트블로우, 스테이플), 로프, 또는 네트로 이용될 수 있다.The molded article may be in various forms such as a film, a sheet, or a fiber, and may be an injection molded article, an extrusion molded article, or a blow molded article. The mold temperature in the case of injection molding may be 130 degreeC or more from a viewpoint of crystallization. In addition, when the molded article is in the form of a film or sheet, it can be produced into various films or sheets by using methods such as unstretched, uniaxial stretch, biaxial stretch, and the like. When the molded article is a fiber, it may be various fibers such as undrawn yarn, drawn yarn, or super drawn yarn, and may be used as a woven fabric, knitted fabric, nonwoven fabric (spunbond, melt blown, staple), rope, or net.
이러한 성형품은 금속접착성이 요구되는 컴퓨터 부속품 등의 전기 또는 전자 부품, 건축 부재, 자동차 부품, 기계 부품, 일용품 또는 화학물질이 접촉하는 부분의 코팅, 산업용 내화학성 섬유 등으로 이용될 수 있다.Such molded articles may be used as coatings for electrical or electronic parts, such as computer accessories requiring metal adhesive properties, building members, automobile parts, mechanical parts, daily necessities or chemical contact parts, industrial chemical resistant fibers, and the like.
이하, 본 발명을 하기 실시예에 의하여 더욱 상세하게 설명한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 범위가 이들만으로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
제조예: PPS의 제조Preparation Example: Preparation of PPS
반응기의 내온 측정이 가능한 써모커플, 및 질소 충전 및 진공을 걸 수 있는 진공라인이 부착된 5 ℓ 반응기에 파라-디요오도벤젠(p-DIB) 5,130 g, 황 450 g을 포함한 혼합물을 180℃로 가열하여 완전히 용융 및 혼합한 후, 220℃ 및 350 Torr의 초기 반응 조건에서 시작하여, 최종 반응온도는 300℃, 압력은 0.6 내지 0.9 Torr까지 단계적으로 온도 상승 및 압력 강하를 4 시간 동안 수행하고, 황을 19 g씩 7 회에 걸쳐 투입하면서 중합반응을 진행하였다. 상기 중합반응이 80 % 진행되었을 때(이러한 중합반응의 진행 정도는 식"(현재 점도/목표 점도)×100"으로, 목표 점도에 대한 현재 점도의 상대 비율로서 측정하였으며, 현재 점도는 중합 진행 중의 샘플을 채취해 점도계로 측정하였다. 또한, 목표 점도는 2,000 poise로 하였다.), 중합중지제로 디페닐 디설파이드 35 g을 첨가하고 10 분 동안 질소 분위기 하에서 반응을 진행한 후, 0.5 Torr 이하로 서서히 진공을 가하여 목표점도에 도달 한 후 반응을 종료하여, 히드록시기를 주쇄 말단에 포함하지 않은 폴리아릴렌 설파이드(PPS) 수지를 합성하였다. 반응이 완료된 수지를 소형 스트랜드 커터기를 사용하여 펠렛 형태로 제조하였다.A mixture containing 5,130 g of para-diiobenzene (p-DIB) and 450 g of sulfur in a 5 L reactor equipped with a thermocouple capable of measuring internal temperature of the reactor and a vacuum line capable of filling with nitrogen and vacuuming was charged at 180 ° C. After the complete melting and mixing by heating to start the initial reaction conditions of 220 ℃ and 350 Torr, the final reaction temperature is 300 ℃, the pressure is 0.6 to 0.9 Torr step by step temperature rise and pressure drop for 4 hours , 19 g of sulfur each time was added seven times to proceed with the polymerization. When the polymerization reaction proceeded at 80% (the degree of progress of the polymerization reaction was expressed by a formula "(current viscosity / target viscosity) x 100", which was measured as a relative ratio of the current viscosity to the target viscosity, and the current viscosity was in the course of polymerization. Samples were taken and measured with a viscometer, and the target viscosity was 2,000 poise.), 35 g of diphenyl disulfide was added as a polymerization terminator, the reaction was carried out under a nitrogen atmosphere for 10 minutes, and then gradually vacuumed to 0.5 Torr or less. After the reaction reached the target viscosity by adding the reaction mixture, the polyarylene sulfide (PPS) resin having no hydroxyl group at the end of the main chain was synthesized. Resin was completed was prepared in pellet form using a small strand cutter.
생성된 PPS 수지는 다음과 같은 방식에 따라 융점(Tm), 수평균분자량(Mn), 분자량 분포(PDI) 및 용융 점도(melt viscosity, 이하 'MV'로 기재)를 측정하였다. 그 결과, 제조한 PPS 수지의 융점은 280℃, Mn은 17,420, PDI는 2.8, MV는 2,150 Poise, 주쇄 결합 요오드 및 유리 요오드 함량은 200 ppm으로 나타났다.The resulting PPS resin was measured for melting point (Tm), number average molecular weight (Mn), molecular weight distribution (PDI) and melt viscosity (hereinafter referred to as 'MV') in the following manner. As a result, the melting point of the prepared PPS resin was 280 ° C, Mn was 17,420, PDI was 2.8, MV was 2,150 Poise, main chain-bonded iodine and free iodine content was 200 ppm.
융점(Tm)Melting Point (Tm)
시차주사 열량분석기(Differential Scanning Calorimeter; DSC)를 이용하여 30℃에서 320℃까지 10 ℃/분의 속도로 승온 후 30℃까지 냉각 후에 다시 30℃에서 320℃까지 10 ℃/분의 속도로 승온하면서 융점을 측정하였다. Using a differential scanning calorimeter (DSC), the temperature was raised from 30 ° C. to 320 ° C. at a rate of 10 ° C./min, cooled to 30 ° C., and then raised again from 30 ° C. to 320 ° C. at a rate of 10 ° C./min. Melting point was measured.
수평균분자량(Mn) 및 분자량 분포(PDI)Number average molecular weight (Mn) and molecular weight distribution (PDI)
PPS 수지를 1-클로로나프탈렌(1-chloronaphthalene)에 0.4 중량%의 농도로 250 ℃에서 25 분간 교반 용해한 샘플을 제조하였다. 이후 고온 GPC(Gel permeation chromatography)시스템(210 )에 상기 샘플을 1 ㎖/분의 유속으로 흘려주면서 분자량이 다른 폴리아릴렌 설파이드를 순차적으로 컬럼 내에서 분리하였다. 이후 RI detector를 이용하여 분리된 폴리아릴렌 설파이드의 분자량별 강도(Intensity)를 측정하였으며, 미리 분자량을 알고 있는 표준시료(Polystyrene)로 검량선을 작성하여, 제조한 PPS 수지의 수평균분자량(Mn) 및 분자량 분포(PDI)를 계산하였다.A sample in which PPS resin was dissolved in 1-chloronaphthalene (1-chloronaphthalene) at a concentration of 0.4% by weight at 250 ° C. for 25 minutes was prepared. Then, the polyarylene sulfides having different molecular weights were sequentially separated in the column while flowing the sample to a high temperature gel permeation chromatography (GPC) system 210 at a flow rate of 1 ml / min. Thereafter, the RI detector was used to measure the intensity of each of the polyarylene sulfides separated by molecular weight, and a calibration curve was prepared from polystyrene. The number average molecular weight (Mn) of the prepared PPS resin was prepared. And molecular weight distribution (PDI).
용융 점도(MV)Melt Viscosity (MV)
용융 점도는 회전 원판 점도계(rotating disk viscometer)로 300 ℃에서 측정하였다. Frequency sweep 방법으로 측정함에 있어, angular frequency를 0.6 rad/s부터 500 rad/s까지 측정하였고, 1.84 rad/s에서의 점도를 용융 점도(MV)로 정의하였다.Melt viscosity was measured at 300 ° C. with a rotating disk viscometer. In measuring by the frequency sweep method, the angular frequency was measured from 0.6 rad / s to 500 rad / s, and the viscosity at 1.84 rad / s was defined as the melt viscosity (MV).
주쇄 결합 요오드 및 유리 요오드 함량(ppm)Main chain-bound iodine and free iodine content (ppm)
주쇄 결합 요오드 및 유리 요오드 함량(ppm)은 PPS 수지를 1,000℃에서 furnace를 이용하여 태운 후 요오드를 이온화하여 증류수에 용해시키는 자동 전처리장치(AQF)를 통해 준비된 샘플을 이온크로마토그래피(ion chromatography)를 통해 미리 분석된 검량 커브를 이용하여 PPS 수지 중 요오드의 함량을 측정하였다.The main chain-bound iodine and free iodine content (ppm) was measured by ion chromatography using an automatic pretreatment device (AQF) in which PPS resin was burned using a furnace at 1,000 ° C and ionized and dissolved in distilled water. The content of iodine in the PPS resin was measured using a calibration curve analyzed in advance.
실시예 1: PPS 수지 조성물의 제조Example 1: Preparation of PPS Resin Composition
이축 스크류 압출기에, 상기 제조예에서 수득한 PPS 수지 100 중량부에, PCT 수지(제조사: SK chemicals사, 제품명: 0302, 중량평균분자량: 56,000, 고유점도(IV): 0.65 ㎗/g, 분광측색계를 이용하여 D65 광원의 경면반사광포함 모드에서 측정한 L값: 90) 9 중량부, 페녹시 수지(제조사: InChem사, 제품명: PKHH, 중량평균분자량: 52,000, 유리전이 온도: 92 ℃) 9 중량부, 에폭시실란 처리된 유리 섬유(제조사: Owens corning사, 제품명: V-910) 25 중량부, 백색 안료로 ZnS(제조사: Sachtleben사, 제품명: Sachtolith) 9 중량부, 엘라스토머(제조사: Arkema사, 제품명: Lotader AX-8900, 글리시딜 메타 아크릴레이트, 아크릴 에스테르 및 에틸렌의 삼원 공중합체) 13 중량부를 첨가하여 PPS 수지 조성물을 제조하였다.PCT resin (manufacturer: SK chemicals, product name: 0302, weight average molecular weight: 56,000, intrinsic viscosity (IV): 0.65 dl / g, spectroscopic side L value measured in a specular reflection mode of a D65 light source using a colorimeter: 90) 9 parts by weight, phenoxy resin (manufacturer: InChem, product name: PKHH, weight average molecular weight: 52,000, glass transition temperature: 92 ° C) 9 Parts by weight, 25 parts by weight of an epoxysilane-treated glass fiber (manufacturer: Owens corning, product name: V-910), 9 parts by weight of ZnS (manufacturer: Sachtleben, product name: Sachtolith) as a white pigment, elastomer (manufacturer: Arkema) , Product name: Lotader AX-8900, tertiary copolymer of glycidyl methacrylate, acrylic ester and ethylene) was added to prepare a PPS resin composition.
이때 사용한 이축 압출기는 SM platek의 직경 40 mm, L/D=44 압출기를 사용하였다. 공정 조건은 스크류 250 rpm, 토출양(feed rate) 60 kg/시, 배럴 온도는 280℃에서 300℃, 토크 60 %로 수행하였다. 원료 투입은 총 세 개의 피더(feeder)를 사용하였으며, 피더 1은 PPS 수지, PCT 수지, 페녹시 수지 및 엘라스토머를, 피더 2는 백색 안료를, 피더 3은 유리 섬유를 각각 분산 투입하여 PPS 수지 조성물을 제조하였다.The twin screw extruder used was a 40 mm diameter SM platek, L / D = 44 extruder. Process conditions were performed with a screw 250 rpm, a feed rate of 60 kg / hour, barrel temperature from 280 ℃ to 300 ℃, torque 60%. A total of three feeders were used to feed the raw materials, and feeder 1 dispersed and added PPS resin, PCT resin, phenoxy resin and elastomer, feeder 2 white pigment, and feeder 3 glass fiber, respectively. Was prepared.
실시예 2 내지 5 및 비교예 1Examples 2 to 5 and Comparative Example 1
하기 표 2에 기재된 바와 같은 성분 및 함량을 이용하여 상기 실시예 1과 동일한 방식으로 PPS 수지 조성물을 제조하였다. A PPS resin composition was prepared in the same manner as in Example 1, using the ingredients and contents as described in Table 2 below.
비교예 2Comparative Example 2
PPS 수지로서 제조예의 PPS 대신 용액중합으로 제조된 PPS(제조사: Celanese사, 제품명: 0205P4, 선형 PPS, 하기 "PPS1"로 기재)을 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방식으로 PPS 수지 조성물을 제조하였다. PPS resin in the same manner as in Example 1, except that PPS (manufactured by Celanese, product name: 0205P4, linear PPS, described below as "PPS1") prepared by solution polymerization was used as the PPS resin in the preparation example. The composition was prepared.
비교예 3Comparative Example 3
PPS 수지로서 제조예의 PPS 대신 용액중합으로 제조된 PPS(제조사: Solvay사, 제품명: P6, 교차형 PPS, 하기 "PPS2"로 기재)을 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방식으로 PPS 수지 조성물을 제조하였다.PPS was prepared in the same manner as in Example 1, except that PPS prepared by solution polymerization instead of PPS in Preparation Example (manufacturer: Solvay, product name: P6, cross-linked PPS, described below as "PPS2") was used. A resin composition was prepared.
비교예 4Comparative Example 4
PCT 수지를 사용하지 않은 것을 제외하고는, 하기 표 2에 기재된 바와 같은 성분 및 함량을 이용하여 상기 실시예 1과 동일한 방식으로 PPS 수지 조성물을 제조하였다. A PPS resin composition was prepared in the same manner as in Example 1, except that no PCT resin was used, using the ingredients and contents as described in Table 2 below.
비교예 5Comparative Example 5
하기 표 2에 기재된 바와 같은 성분 및 함량을 이용하여 상기 실시예 1과 동일한 방식으로 PPS 수지 조성물을 제조하였다.A PPS resin composition was prepared in the same manner as in Example 1, using the ingredients and contents as described in Table 2 below.
비교예 6Comparative Example 6
PCT 수지 대신 폴리에틸렌 테레프탈레이트(polyethylene terephthalate; PET) 수지(제조사: SK chemical사, 제품명: BB 8055)를 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방식으로 PPS 수지 조성물을 제조하였다.A PPS resin composition was prepared in the same manner as in Example 1, except that polyethylene terephthalate (PET) resin (manufacturer: SK Chemical, product name: BB 8055) was used instead of PCT resin.
상기 실시예 1 내지 5 및 비교예 1 내지 6에서 사용된 성분들의 입수처를 정리하여 하기 표 1에 나타내었다. Table 1 summarizes the availability of the components used in Examples 1 to 5 and Comparative Examples 1 to 6.
성분ingredient 제품명product name 제조사manufacturer
AA 제조예의 PPSPPS of manufacture example -- --
BB 용액 중합 PPS1Solution Polymerization PPS1 0205P40205P4 CelaneseCelanese
CC 용액 중합 PPS2Solution Polymerized PPS2 P6P6 SolvaySolvay
DD PCTPCT 03020302 SK chemicalsSK chemicals
EE PETPET BB 8055BB 8055 SK chemicalsSK chemicals
FF 페녹시 수지Phenoxy resin PKHHPKHH InChemInchem
GG 유리섬유Fiberglass OCV-910OCV-910 Owens corningOwens corning
HH 백색 안료White pigment SachtolithSachtolith SachtlevenSachtleven
II 엘라스토머Elastomer Lotader AX-8900Lotader AX-8900 ArkemaArcema
실험예Experimental Example
상기 실시예 및 비교예에서 제조한 PPS 수지 조성물을 대상으로 하기 기재된 바에 따라 물성을 측정하였으며, 측정 결과를 하기 표 2에 나타내었다.Physical properties of the PPS resin compositions prepared in Examples and Comparative Examples were measured as described below, and the measurement results are shown in Table 2 below.
먼저, 실시예 및 비교예에서 제조한 PPS 수지 조성물을 310℃에서 각각 사출하여 사출 시편을 제조하였다. First, injection specimens were prepared by injecting the PPS resin compositions prepared in Examples and Comparative Examples at 310 ° C., respectively.
(1) 아웃 가스 함량(1) out gas content
사출 성형기 2단 금형의 고정 금형과 이동 금형 사이에 특정 에칭 처리된 알루미늄 시편(가로: 70 mm, 세로: 18 mm 및 높이: 2 mm)을 안착시켰다. 2단 금형 사이에 실시예 및 비교예에서 제조한 PPS 수지 조성물을 각각 넣어 80 톤 Engel 사출기에서, 사출속도 50 mm/s, 사출압 120 ㎫ 및 금형온도 150℃에서 인서트 사출하고, 금형으로부터 분리함으로써 금속접착강도 측정용 시편(가로 70 mm, 세로 10 mm 및 높이 3 mm)을 제조하였다(도 1). 이후 사출 시편(2 g)을 20 ㎖ 밀봉 바이알(vial)에 넣고 밀봉시킨 후 HS(Head Space) 장비로 260℃에서 30 분간 가열한 후 발생한 가스를 자동으로 GC/MS(gas chromatography-mass Spectrometer) 장비로 보냈다. 이후, 각 성분을 캐필러리 컬럼으로 분리한 후 정성 분석하고, 표준 물질로 벤조티아졸(benzothiazole)을 사용하여 시료 내 각 성분의 함량을 대체 정량 분석하였다.A specific etched aluminum specimen (width: 70 mm, length: 18 mm and height: 2 mm) was seated between the stationary mold and the moving mold of the injection molding machine two-stage mold. By inserting the PPS resin compositions prepared in Examples and Comparative Examples, respectively, between the two-stage molds, insert injection was performed at an injection speed of 50 mm / s, an injection pressure of 120 MPa and a mold temperature of 150 ° C. in an 80 ton Engel injection machine, and then separated from the mold. Specimens for measuring metal adhesion strength (70 mm wide, 10 mm long and 3 mm high) were prepared (FIG. 1). Then, the injection specimen (2 g) was put into a 20 ml sealed vial and sealed, and the gas generated after heating for 30 minutes at 260 ° C. with a HS (Head Space) equipment was automatically gas chromatography-mass spectrometer (GC / MS). Sent to the equipment. Thereafter, each component was separated by a capillary column and qualitatively analyzed, and benzothiazole was used as a standard substance to quantitatively analyze the content of each component in the sample.
(2) 염소 함량 (2) chlorine content
제조예의 PPS, 용액 중합 PPS1 또는 PPS2 수지의 사출 시편(상기 (1)의 사출 시편) 50 mg을 AQF(Auto Quick Furnace)를 이용해 1,000℃에서 가습을 하면서 유기물을 완전 연소시키고 연소가스를 흡수용액(과산화수소수 900 ppm)에 포집한 후 이온 크로마토그래피(ion chromatography, Auto Quick Furnace)로 자동주입 후 사출 시편의 염소 함량을 측정하였다.50 mg of PPS, solution-polymerized PPS1 or PPS2 resin of the preparation example (injection specimen of (1)) was humidified at 1,000 ° C. using AQF (Auto Quick Furnace) while completely burning the organic matter and absorbing the combustion gas. After collecting in 900 ppm hydrogen peroxide solution, the chlorine content of the injection specimen was measured after auto-injection by ion chromatography (ion chromatography, Auto Quick Furnace).
(3) 인장 강도 (3) tensile strength
ISO 527법에 따라, 상기 (1)의 사출 시편의 인장강도를 측정하였다.According to the ISO 527 method, the tensile strength of the injection specimen of (1) was measured.
(4) 금속접착강도(4) metal bonding strength
상기 (1)의 사출 시편의 금속접착강도를 ASTM D 3163 법에 따라 측정하였다.The metal adhesive strength of the injection specimen of (1) was measured according to the ASTM D 3163 method.
(5) L값(5) L value
분광측색계(Konica Minolta, 3600D)를 이용하여 D65 광원의 경면반사광포함(specular component included, SCI) 모드에 따라 L값을 측정하였다. L값이 높을수록 백색도가 우수하다.L value was measured according to the specular component included (SCI) mode of the D65 light source using a spectrophotometer (Konica Minolta, 3600D). The higher the L value, the better the whiteness.
(6) 양극산화반응(Anodizing)(6) Anodizing
상기 (1)에서 성형한 시편을 50℃의 수산화나트륨(NaOH) 용액에 30 초간 담지한 후, 98 중량%의 황산 수용액과 84 중량%의 인산 수용액을 1:7 부피비로 섞은 용액에 2 분 동안 체류시켰다. 이후 상온의 묽은 황산 용액에서 20 V의 전류를 흘려 20 분 동안 산화 공정을 거친 후 수세 처리를 한다. 이후 (1)과 동일한 방법으로 금속접착 강도를 측정하고, (5)와 동일한 방법으로 L값을 측정한 후, 양극 산화공정 전, 후 두 값의 차이를 측정하였다. 차이가 적을수록 내산성이 우수하다고 판단할 수 있다.The specimen molded in (1) was immersed in a 50 ° C. sodium hydroxide (NaOH) solution for 30 seconds, and then mixed in a solution containing 98% by weight sulfuric acid solution and 84% by weight phosphoric acid solution in a 1: 7 volume ratio for 2 minutes. Stayed. Thereafter, a 20 V current is passed in a dilute sulfuric acid solution at room temperature, followed by an oxidation process for 20 minutes, and then washed with water. Thereafter, the metal adhesive strength was measured in the same manner as in (1), and the L value was measured in the same manner as in (5), and then the difference between the two values before and after the anodic oxidation process was measured. The smaller the difference, the better the acid resistance.
성분 (중량부)Ingredients (parts by weight) 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예 4Example 4 실시예 5Example 5 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4 비교예 5Comparative Example 5 비교예 6Comparative Example 6
PPSPPS AA 100100 100100 100100 100100 100100 100100 -- -- 100100 100100 100100
BB -- -- -- -- -- -- 100100 -- -- -- --
CC -- -- -- -- -- -- -- 100100 -- -- --
폴리 에스터polyester DD 99 99 1111 55 1414 1919 99 99 -- 4343 --
EE -- -- -- -- -- -- -- -- -- -- 99
FF 99 99 1111 88 99 1919 99 99 88 1111 99
GG 2525 3636 6464 2424 2626 186186 2525 2525 2323 3232 2525
HH 99 99 1111 88 99 1919 99 99 88 1111 99
II 1313 1515 1818 1313 1414 3030 1313 1313 1212 1818 1313
물성Properties 아웃가스함량(ppm)Outgas Content (ppm) 289289 272272 267267 282282 291291 255255 665665 12921292 270270 303303 301301
염소 함량 (ppm)Chlorine Content (ppm) 3232 3333 3131 3131 3030 2929 891891 15621562 3131 3030 3030
인장 강도(㎫)Tensile Strength (MPa) 9595 109109 135135 9898 9191 149149 9494 9999 102102 7373 9090
금속접착강도(㎫)Metal Bonding Strength (MPa) 6868 6868 6262 6666 7070 5050 6666 6060 5555 7171 7373
산화 공정 후 금속접착강도(㎫)Metal adhesion strength after oxidation process (MPa) 6666 6565 5959 6363 6868 4848 5252 5151 5151 6969 6666
금속 접착 강도(㎫) Metal adhesive strength (MPa) -2-2 -3-3 -3-3 -3-3 -2-2 -2-2 -14-14 -9-9 -4-4 -2-2 -7-7
L 값L value 91.191.1 91.291.2 91.591.5 90.890.8 91.891.8 91.791.7 91.991.9 71.371.3 9090 92.092.0 87.387.3
양극 산화공정 후 L 값L value after anodizing 91.091.0 91.091.0 91.291.2 90.790.7 91.791.7 91.491.4 87.587.5 71.071.0 89.889.8 91.891.8 85.985.9
L값 L value -0.1-0.1 -0.2-0.2 -0.3-0.3 -0.1-0.1 -0.1-0.1 -0.3-0.3 -4.4-4.4 -0.3-0.3 -0.2-0.2 -0.2-0.2 -1.4-1.4
표 2에서 보는 바와 같이, 본 발명에 따른 수지 조성물은 금속접착 강도가 60 내지 70 ㎫로 유리 섬유를 과량 포함하는 비교예 1의 50 ㎫보다 현저히 우수한 금속접착능을 나타냈다. 또한, 제조예에서 제조된 PPS를 포함하는 실시예 1 내지 5는 PPS1 또는 PPS2를 포함하는 비교예 2 및 3에 비해 아웃 가스 함량이 최대 약 4배 감소된 효과를 보였다. 또한, 염소 함량은 실시예 1 내지 5가 35 ppm 이하인 반면, 비교예 2는 891 ppm, 비교예 3은 1562 ppm으로 현저히 높다. 아울러 양극산화 공정 후 L값은 실시예 1 내지 5가 90 이상인 반면, 비교예 2는 90 이하로 백색도가 급격하게 저하됐다.As shown in Table 2, the resin composition which concerns on this invention showed the metal adhesive strength remarkably superior to 50 MPa of the comparative example 1 which contains an excess glass fiber with metal adhesive strength of 60-70 MPa. In addition, Examples 1 to 5 including PPS prepared in Preparation Example showed an out gas content up to about 4 times lower than Comparative Examples 2 and 3 including PPS1 or PPS2. In addition, the chlorine content was remarkably high while Examples 1 to 5 were 35 ppm or less, while Comparative Example 2 was 891 ppm and Comparative Example 3 was 1562 ppm. In addition, the L value after the anodization process, while Examples 1 to 5 were 90 or more, while Comparative Example 2 had a sharp decrease in whiteness to 90 or less.
더불어, PCT 수지를 포함하지 않는 비교예 4와 비교하여, 실시예 1 내지 5의 수지 조성물은 금속 접착 강도가 60 내지 70 ㎫로 향상된 금속 접착능을 나타냈고, 비교예 4는 55 ㎫로 금속 접착 강도가 현저히 낮았다.In addition, compared with Comparative Example 4, which does not contain PCT resin, the resin compositions of Examples 1 to 5 exhibited improved metal adhesive strength of 60 to 70 MPa, and Comparative Example 4 was 55 MPa. The strength was significantly lower.
또한, PCT 수지를 과량 첨가한 비교예 5는 인장강도가 저하됨을 확인할 수 있었다. 한편, PCT 수지 대신 PET 수지를 포함하는 비교예 6은 금속 접착능은 높으나 L값이 낮았고, 산화 공정 이후 L값이 실시예 1 내지 5에 비해 현저하게 떨어졌다.In addition, Comparative Example 5, in which the PCT resin was added in excess, confirmed that the tensile strength decreased. On the other hand, Comparative Example 6 containing a PET resin instead of PCT resin has a high metal adhesion capacity, but the L value was low, the L value was significantly lower than the Examples 1 to 5 after the oxidation process.
따라서, 본 발명에 따른 수지 조성물은 아웃 가스 함량을 감소시키면서도 우수한 백색도, 내산성 및 금속 접착능을 나타내므로, 사출 인서트 성형으로 일체화되는 휴대폰, 전자부품, 자동차 부품 등의 다양한 분야에서 유용하게 사용될 수 있다. 또한, 불순물이 포함되지 않아 전자 제품의 성능 저하를 방지할 수 있다.Therefore, the resin composition according to the present invention exhibits excellent whiteness, acid resistance and metal adhesion while reducing outgas content, and thus can be usefully used in various fields such as mobile phones, electronic parts, automobile parts, etc., which are integrated with injection insert molding. . In addition, since impurities are not contained, deterioration of the performance of the electronic product can be prevented.

Claims (20)

  1. 폴리아릴렌 설파이드; 및 하기 화학식 1로 표시되는 반복단위를 포함하는 폴리사이클로헥실렌디메틸렌테레프탈레이트(polycyclohexylenedimethyleneterephthalate)를 포함하고, 아웃가스 함량이 300 ppm 이하인 수지 조성물:Polyarylene sulfides; And a polycyclohexylenedimethylene terephthalate comprising a repeating unit represented by the following Chemical Formula 1, wherein the resin composition has an outgas content of 300 ppm or less:
    [화학식 1][Formula 1]
    Figure PCTKR2017000612-appb-I000003
    Figure PCTKR2017000612-appb-I000003
  2. 제1항에 있어서,The method of claim 1,
    상기 폴리사이클로헥실렌디메틸렌테레프탈레이트가 폴리아릴렌 설파이드 100 중량부에 대하여 0.5 내지 50 중량부의 양으로 포함되는, 수지 조성물.The polycyclohexylenedimethylene terephthalate is contained in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of polyarylene sulfide.
  3. 제1항에 있어서,The method of claim 1,
    상기 폴리사이클로헥실렌디메틸렌테레프탈레이트는 중량평균분자량이 10,000 내지 200,000인, 수지 조성물.The polycyclohexylenedimethylene terephthalate has a weight average molecular weight of 10,000 to 200,000, the resin composition.
  4. 제1항에 있어서,The method of claim 1,
    상기 폴리아릴렌 설파이드가 주쇄에 결합된 요오드 및 유리 요오드를 포함하며, 상기 주쇄에 결합된 요오드 및 유리 요오드의 함량이 10 내지 10,000 ppm인, 수지 조성물.The polyarylene sulfide comprises iodine and free iodine bonded to the main chain, the content of iodine and free iodine bonded to the main chain is 10 to 10,000 ppm.
  5. 제1항에 있어서,The method of claim 1,
    상기 폴리아릴렌 설파이드는 염소 함량이 300 ppm 이하인, 수지 조성물.The polyarylene sulfide has a chlorine content of 300 ppm or less.
  6. 제1항에 있어서,The method of claim 1,
    상기 수지 조성물이 페녹시 수지, 엘라스토머, 충진재, 충격 흡수제, 접착력 향상제, 안정제, 안료, 가소제, 활제 및 핵제로 이루어진 군으로부터 선택되는 1종 이상의 성분을 더 포함하는, 수지 조성물.The resin composition further comprises at least one component selected from the group consisting of phenoxy resins, elastomers, fillers, shock absorbers, adhesion promoters, stabilizers, pigments, plasticizers, lubricants and nucleating agents.
  7. 제6항에 있어서,The method of claim 6,
    상기 페녹시 수지의 중량평균분자량이 10,000 내지 250,000이고, 유리 전이 온도가 50 내지 130 ℃인, 수지 조성물.The weight average molecular weight of the phenoxy resin is 10,000 to 250,000, the glass transition temperature is 50 to 130 ℃, the resin composition.
  8. 제6항에 있어서,The method of claim 6,
    상기 페녹시 수지가 하기 화학식 2로 표시되는, 수지 조성물:Resin composition, wherein the phenoxy resin is represented by the following formula (2):
    [화학식 2][Formula 2]
    Figure PCTKR2017000612-appb-I000004
    Figure PCTKR2017000612-appb-I000004
    상기 화학식 2에서,In Chemical Formula 2,
    n은 100 내지 900의 정수이다.n is an integer from 100 to 900.
  9. 제6항에 있어서,The method of claim 6,
    상기 엘라스토머가 폴리염화비닐계 엘라스토머, 폴리올레핀계 엘라스토머, 폴리우레탄계 엘라스토머, 폴리에스테르계 엘라스토머, 폴리아미드계 엘라스토머, 폴리부타디엔계 엘라스토머 및 글리시딜 메타 아크릴레이트와 메틸 아크릴 에스테르, 에틸렌의 삼원 공중합체 엘라스토머로 이루어진 군에서 선택되는 1종 이상의 열가소성 엘라스토머인, 수지 조성물.The elastomers are polyvinyl chloride elastomers, polyolefin elastomers, polyurethane elastomers, polyester elastomers, polyamide elastomers, polybutadiene elastomers, glycidyl methacrylates, methyl acrylic esters, and ethylene terpolymers of ethylene. The resin composition, which is at least one thermoplastic elastomer selected from the group consisting of:
  10. 제6항에 있어서,The method of claim 6,
    상기 충진재가 유리 섬유, 탄소 섬유, 붕소 섬유, 유리 비드, 유리 플레이크, 활석, 탈크 및 탄산칼슘으로 이루어진 군으로부터 선택되는 1종 이상인, 수지 조성물.The filler is at least one member selected from the group consisting of glass fibers, carbon fibers, boron fibers, glass beads, glass flakes, talc, talc and calcium carbonate.
  11. 제10항에 있어서,The method of claim 10,
    상기 유리 섬유가 에폭시 실란, 아미노 실란 및 이의 조합으로 이루어진 군으로부터 선택된 실란으로 처리된 유리 섬유인, 수지 조성물.And the glass fiber is a glass fiber treated with a silane selected from the group consisting of epoxy silane, amino silane and combinations thereof.
  12. 제1항에 있어서,The method of claim 1,
    상기 수지 조성물의 염소 함량이 300 ppm 이하인, 수지 조성물.The resin composition whose chlorine content of the said resin composition is 300 ppm or less.
  13. 제1항에 있어서,The method of claim 1,
    상기 수지 조성물은 ISO 527에 따라 측정한 인장강도 값이 80 ㎫ 이상인, 수지 조성물.The resin composition has a tensile strength value of 80 MPa or more as measured according to ISO 527.
  14. 제1항에 있어서,The method of claim 1,
    상기 수지 조성물은 ASTM D 3163에 따라 측정한 금속접착강도 값이 60 ㎫ 이상인, 수지 조성물.The resin composition has a resin adhesive strength value of 60 MPa or more, measured according to ASTM D 3163.
  15. 제1항에 있어서,The method of claim 1,
    상기 수지 조성물은 D65 광원의 경면반사광포함(specular component included, SCI) 모드에 따라 측정한 L값이 89 이상인, 수지 조성물.The resin composition has a L value of 89 or more measured according to the specular component included (SCI) mode of the D65 light source.
  16. 제1항에 있어서,The method of claim 1,
    상기 수지 조성물은 양극산화처리(anodizing) 후 ASTM D 3163에 따라 측정한 금속접착강도값이 55 ㎫ 이상인, 수지 조성물.The resin composition has a metal adhesive strength value of 55 MPa or more measured according to ASTM D 3163 after anodizing.
  17. 제1항에 있어서,The method of claim 1,
    상기 수지 조성물은 양극산화처리(anodizing) 후 D65 광원의 경면반사광포함(specular component included, SCI) 모드에 따라 측정한 L값이 88 이상인, 수지 조성물.The resin composition has a L value of 88 or more measured according to the specular component included (SCI) mode of the D65 light source after anodizing.
  18. 제1항 내지 제17항 중 어느 한 항의 수지 조성물을 성형하여 제조된 성형품.The molded article manufactured by shape | molding the resin composition of any one of Claims 1-17.
  19. 제18항에 있어서,The method of claim 18,
    상기 성형품은 금속접착성이 요구되는 전기 또는 전자 부품인, 성형품.Wherein the molded article is an electrical or electronic component requiring metal adhesion.
  20. 제18항에 있어서,The method of claim 18,
    상기 성형품은 금속접착성이 요구되는 자동차 부품인, 성형품.The molded article is a molded article, which is an automotive part requiring metal adhesiveness.
PCT/KR2017/000612 2016-02-15 2017-01-18 Polyarylene sulfide composition having excellent adhesion to metals WO2017142217A1 (en)

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