WO2017142217A1 - Composition de poly(sulfure d'arylène) présentant une excellente adhérence à des métaux - Google Patents

Composition de poly(sulfure d'arylène) présentant une excellente adhérence à des métaux 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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English (en)
Korean (ko)
Inventor
김해리
신종욱
정명욱
안병우
오형근
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이니츠 주식회사
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Priority to CN201780008608.0A priority Critical patent/CN108603030B/zh
Priority to JP2018543169A priority patent/JP6707655B2/ja
Publication of WO2017142217A1 publication Critical patent/WO2017142217A1/fr

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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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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de poly(sulfure d'arylène) ayant une faible propriété de dégazage, et ayant une excellente brillance, une résistance aux acides et une adhérence aux métaux. La composition de résine de poly(sulfure d'arylène) selon la présente invention présente une excellente brillance, résistance aux acides et adhérence aux métaux ainsi qu'une faible propriété de dégazage, et peut donc être utilisée comme composition de résine pour la fabrication d'un produit nécessitant une précision de moulage.
PCT/KR2017/000612 2016-02-15 2017-01-18 Composition de poly(sulfure d'arylène) présentant une excellente adhérence à des métaux WO2017142217A1 (fr)

Priority Applications (2)

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CN201780008608.0A CN108603030B (zh) 2016-02-15 2017-01-18 对金属具有优异粘附性的聚芳硫醚组合物
JP2018543169A JP6707655B2 (ja) 2016-02-15 2017-01-18 金属に対して優れた接着性を有するポリアリーレンスルフィド組成物

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KR1020160017133A KR20170095569A (ko) 2016-02-15 2016-02-15 금속과의 접착성이 우수한 폴리아릴렌 설파이드 조성물
KR10-2016-0017133 2016-02-15

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WO2017142217A1 true WO2017142217A1 (fr) 2017-08-24

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JP (1) JP6707655B2 (fr)
KR (1) KR20170095569A (fr)
CN (1) CN108603030B (fr)
TW (1) TW201800486A (fr)
WO (1) WO2017142217A1 (fr)

Citations (5)

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US5023293A (en) * 1989-02-09 1991-06-11 Mitsubishi Rayon Co., Ltd. Polyarylene sulfide resin paint composition
KR930012984A (ko) * 1991-12-31 1993-07-21 이승동 내열성이 우수한 폴리에스터 수지조성물
US20050269011A1 (en) * 2004-06-02 2005-12-08 Ticona Llc Methods of making spunbonded fabrics from blends of polyarylene sulfide and a crystallinity enhancer
KR20110102226A (ko) * 2010-03-10 2011-09-16 에스케이케미칼주식회사 아웃 가스 발생량이 적은 폴리아릴렌 설파이드 및 이의 제조 방법
KR20140005493A (ko) * 2012-07-04 2014-01-15 에스케이케미칼주식회사 폴리아릴렌 설파이드계 수지 조성물 및 성형품

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JPH04132765A (ja) * 1990-09-25 1992-05-07 Dainippon Ink & Chem Inc 樹脂組成物
JP3206212B2 (ja) * 1993-05-20 2001-09-10 東レ株式会社 ポリフェニレンスルフィド樹脂組成物および複合成形品
JP2000204341A (ja) * 1999-01-11 2000-07-25 Nkk Corp 熱可塑性樹脂フィルムラミネ―ト金属板用接着剤
JP5278367B2 (ja) * 2010-04-12 2013-09-04 新日鐵住金株式会社 有機樹脂ラミネート鋼板
JP2013181043A (ja) * 2012-02-29 2013-09-12 Dic Corp ポリアリーレンスルフィド樹脂組成物および成形体
JP6655392B2 (ja) * 2013-08-09 2020-02-26 Dic株式会社 ポリアリーレンスルフィド樹脂組成物及びその成形品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5023293A (en) * 1989-02-09 1991-06-11 Mitsubishi Rayon Co., Ltd. Polyarylene sulfide resin paint composition
KR930012984A (ko) * 1991-12-31 1993-07-21 이승동 내열성이 우수한 폴리에스터 수지조성물
US20050269011A1 (en) * 2004-06-02 2005-12-08 Ticona Llc Methods of making spunbonded fabrics from blends of polyarylene sulfide and a crystallinity enhancer
KR20110102226A (ko) * 2010-03-10 2011-09-16 에스케이케미칼주식회사 아웃 가스 발생량이 적은 폴리아릴렌 설파이드 및 이의 제조 방법
KR20140005493A (ko) * 2012-07-04 2014-01-15 에스케이케미칼주식회사 폴리아릴렌 설파이드계 수지 조성물 및 성형품

Also Published As

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CN108603030B (zh) 2021-06-29
KR20170095569A (ko) 2017-08-23
TW201800486A (zh) 2018-01-01
CN108603030A (zh) 2018-09-28
JP2019504921A (ja) 2019-02-21
JP6707655B2 (ja) 2020-06-10

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