WO2019059544A1 - Polyester resin composition - Google Patents

Polyester resin composition Download PDF

Info

Publication number
WO2019059544A1
WO2019059544A1 PCT/KR2018/009819 KR2018009819W WO2019059544A1 WO 2019059544 A1 WO2019059544 A1 WO 2019059544A1 KR 2018009819 W KR2018009819 W KR 2018009819W WO 2019059544 A1 WO2019059544 A1 WO 2019059544A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
polyester resin
nucleating agent
resin composition
parts
Prior art date
Application number
PCT/KR2018/009819
Other languages
French (fr)
Korean (ko)
Inventor
이명세
김도균
김태영
신종욱
Original Assignee
에스케이케미칼 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 에스케이케미칼 주식회사 filed Critical 에스케이케미칼 주식회사
Publication of WO2019059544A1 publication Critical patent/WO2019059544A1/en

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • 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
    • C08K3/38—Boron-containing compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

Definitions

  • the present invention relates to a polyester resin composition which exhibits improved crystallization speed and exhibits excellent releasability and mechanical properties.
  • Polyester resins are widely used as reinforcing plastics, paints, films, molding resins, or textile materials for clothing due to their relatively excellent mechanical strength and elastic strength.
  • PCT polycyclohexanediyldimethylene terephthalate
  • Glass fi ber glass fiber
  • the PCT material has a slow crystallization rate and is liable to cause defective molding when it is not sufficiently deflected during injection molding. Further, when sufficient aging time is given for prevention of mold release defects, the entire molding cycle is delayed. This can hinder the application of PCT materials to a variety of applications because it can reduce the productivity of injection molding or component manufacturers.
  • the inventor of the present invention has succeeded in manufacturing a polyester resin composition having improved crystallization speed, excellent releasability and mechanical properties, and succeeded in producing the polyester resin composition. It can be applied to a variety of electric / electronic products or automobile connectors, switches, relays, jacks, IC sockets, AC parts, presser sensors or housings which require excellent releasability and mechanical properties along with rapid crystallization speed. Completed.
  • polyester As a synthetic polymer prepared by polycondensation of a carboxylic acid with one or more diol compounds, including " coplyester ".
  • repeating unit in the polyester means a unit structure having a diol-derived functional group or carboxylic acid-derived functional group bonded through a carbonyloxy group.
  • an inorganic nucleating agent having an excellent effect of improving the crystallization rate in the production of a polyester resin composition using a polyester resin and a filler, and an organic nucleating agent capable of compensating mechanical properties and releasability of the resin composition upon use of the inorganic nucleating agent
  • the crystallization speed can be increased, and the mechanical properties and releasability can be simultaneously improved.
  • the polyester resin composition according to one embodiment of the present invention is a polyester resin composition
  • (iii) it comprises as a nucleating agent, inorganic nitride-based nucleating agent, from 0.01 to 2 parts by weight of 0.92g / cm 3 or more high-density polyethylene (HDPE) based organic nucleating agent, 0.1 to 5 parts by weight.
  • inorganic nitride-based nucleating agent from 0.01 to 2 parts by weight of 0.92g / cm 3 or more high-density polyethylene (HDPE) based organic nucleating agent, 0.1 to 5 parts by weight.
  • HDPE high-density polyethylene
  • the polyester resin is produced by polymerizing a dicarboxylic acid-based compound containing terephthalic acid and a diol compound containing 1,4-cyclo- A repeating unit derived from a dicarboxylic acid-based compound containing the terephthalic acid and a repeating unit derived from a diol compound containing a 1,4-cyclohexanedic acid dimethane.
  • the repeating unit derived from a dicarboxylic acid-based compound is a repeating unit derived from a dicarboxylic acid or an ester thereof .
  • the dicarboxylic acid may specifically be an aromatic dicarboxylic acid having 8 to 20 carbon atoms or an aliphatic dicarboxylic acid having 4 to 20 carbon atoms. More specifically, terephthalic acid (TPA), isophthalic acid (IPA ) Or 2,6-naphthalenedicarboxylic acid (2,6-NDA).
  • TPA terephthalic acid
  • IPA isophthalic acid
  • 2,6-NDA 2,6-naphthalenedicarboxylic acid
  • the dicarboxylic acid ester compound may be an aromatic dicarboxylic acid having 8 to 20 carbon atoms or an ester of an aliphatic dicarboxylic acid having 4 to 20 carbon atoms. More specifically, dimethyl terephthalate (DMT) , Dimethyl isophthalate (DMI), or dimethyl 2,6-naphthalenedicarboxylate (2,6-NDC).
  • DMT dimethyl terephthalate
  • DMI Dimethyl isophthalate
  • 2,6-NDC dimethyl 2,6-naphthalenedicarboxylate
  • the polyester resin in the polyester resin composition according to one embodiment of the present invention, can be produced by controlling the kind and content of the dicarboxylic acid-based compound used in the production thereof, so that the polyester resin is excellent in mechanical properties, heat resistance, And can exhibit more improved characteristics.
  • the repeating unit derived from the dicarboxylic acid-based compound may contain 80 mol% or more of repeating units derived from terephthalic acid or its ester compound based on the total moles of the repeating units derived from the dicarboxylic acid-based compound.
  • the repeating unit derived from the dicarboxylic acid-based compound when applied to a polyester resin composition, it exhibits improved electrical insulation and molding processability, and can maintain excellent initial mechanical properties even in a high temperature and high humidity environment, and exhibits excellent crystallinity at low temperature molding.
  • the polyester resin may contain a repeating unit derived from a dicarboxylic acid-based compound as a repeating unit represented by the following formula (1), wherein at least 80 mol% of the repeating unit may be a repeating unit derived from terephthalic acid, as is to be Ar 1 is a 1,4-phenylene group in the repeating unit of formula I:
  • Ar 1 is a substituted or unsubstituted arylene group having 6 to 18 carbon atoms.
  • the repeating unit derived from the dicarboxylic acid- 80 to 100 mol% of repeating units derived from terephthalic acid or its ester compound, and 0 to 20 mol% of repeating units derived from isophthalic acid or its ester compound, based on the total molar amount of the repeating units derived from the dicarboxylic acid compound.
  • the repeating unit derived from a diol compound may contain repeating units derived from 1,4-cyclohexanedimethanol. Since the repeating unit derived from 1,4-cyclohexane dimethane contains a cyclic structure having 6 carbon atoms, the repeating unit derived from 1,4-cyclohexane dimethane has excellent electrical insulation as compared with a resin containing a phenylene group having non-covalent electrons in a molecular chain such as a polycarbonate resin, As a result, when applied to a polyester resin composition comprising the polyester resin, the electrical insulation can be greatly improved.
  • the repeating unit derived from the 1,4-cyclohexanedimethanemethane is present in an amount of 5 mol% or more, specifically 5 to 100 mol%, more specifically, 60 mol% or more, based on the total moles of repeating units derived from the diol compound constituting the polyester resin To 100 mol%.
  • electrical insulation and heat resistance can be greatly improved while maintaining excellent mechanical properties of the polyester resin composition.
  • the repeating unit derived from a diol compound may be a repeating unit derived from the above-mentioned 1,4-cyclohexanedimethanol-derived repeating unit, such as ethylene glycol, diethylene glycol, 1,4-butanediol, Or neopentyl glycol, and other repeating units derived from a di-based compound.
  • the polyester resin comprises a repeating unit represented by the following general formula (2), wherein in the general formula (2), the repeating unit in which R 1 is cyclonuclearcyclinodimethylene and u is 0 is a repeating unit derived from the repeating unit derived from the diol compound Of recurring units derived from an ethylene-based recurring unit which can further improve the inner layer intrinsic property of the polyester resin, in addition to the repeating unit derived from a diol compound, It can be included in the negative amount:
  • R 1 is a substituted or unsubstituted, linear, branched or cyclic alkylene group having 1 to 10 carbon atoms,
  • R 2 is a substituted or unsubstituted, linear or branched alkylene group having 1 to 10 carbon atoms
  • Y is -O-, -NH- or -S-,
  • u is an integer of 0 or 1.
  • the polyester resin may be a polycycloalkanediyldimethylene terephthalate resin prepared by polycondensation of terephthalic acid and 1,4-cyclohexanedimethanemethane, and the 1,4-cyclohexanedimethanol
  • a part of ethylene glycol is copolymerized in an amount of not more than 1 mol% based on 100 mol of a repeating unit derived from a diol compound, or a part of isophthalic acid is copolymerized with terephthalic acid in an amount of not more than 20 mol% By weight.
  • the polycyclohexanediyldimethylene terephthalate resin has a crystallization speed much faster than that of polyethylene terephthalate (PET), although it is later than polybutylene terephthalate (PBT), has high heat resistance while being injection-molding capable, and relatively high in price competitiveness Potential application possibilities are very high. Further, except for the liquid crystal polymer, it is a polymer having the highest melting point among the existing polyester resins, Has a low water absorption rate as compared with a polyacrylate (PA) type polymer and is excellent in discoloration resistance due to heat. Accordingly, when the polyester resin composition according to the present invention contains the polycyclohexanediyl methylene terephthalate resin as the polyester resin, heat resistance and mechanical strength can be greatly improved while maintaining the tensile strength.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • the polyester resin may have an intrinsic viscosity of 0.50 to 1.2 dl / g converted from a viscosity measured at 35 ° C after dissolving in a solvent 0-chlorophenol (0CP).
  • an intrinsic viscosity within the above-mentioned range, there is no fear of deterioration of mechanical properties due to an appropriate molecular weight, and excellent blending efficiency and moldability can be exhibited.
  • Mw weight-average molecular weight
  • Tg glass transition temperature
  • the polyester resin may be contained in an amount of 60 to 80% by weight based on the total weight of the concrete, specifically, the polyester resin, the filler, and optionally the total amount of the impact reinforcing agent described later, And 60 to 70% by weight, considering that the improvement effect of controlling the polyester content is excellent.
  • the content is less than 60% by weight or exceeds 80% by weight, the releasability may be lowered.
  • the layer transfer material serves to improve the inner layer toughness of the polyester resin composition and can be used without any particular limitation as long as it is usually used for producing a polyester resin composition.
  • the polyester resin composition according to one embodiment of the invention may include an inorganic layer transfer material.
  • the inorganic layer transfer material examples include glass fiber, carbon fiber, boron fiber, glass bead, glass flake, talc, carbon black, clay, mica, wollastonite, calcium titanate whisker, aluminum borate Aluminum boric acid whisker, zinc oxide whisker, or calcium whisker. Any one or two or more of these may be used.
  • the form of the filler is not particularly limited. However, considering the remarkable improvement effect of the use of the layer transfer material and the shape control, among the inorganic layer transfer materials, glass fiber, wollastonite, calcium titanate (calcium titanate whisker, or aluminum boric acid whisker. More specifically, it is possible to improve the moldability and to improve mechanical properties such as tensile strength, bending strength and bending elastic modulus of the molded article Glass fibers can be used in that heat resistance such as heat distortion temperature can be improved. When glass fiber is used as the filler, a glass fiber in the form of a filament, a thread, a fiber or a whisker may be used.
  • the glass fibers may have an average length of 0.1 to 20 mm, 0.3 to 10 or 2 to 5 mm, and an aspect ratio ([L (average fiber length) / D (average fiber diameter)]) Can be from 10 to 2000, or from 30 to 1000. It is possible to exhibit an effect of improving the mechanical strength more than when the above aspect ratio conditions are satisfied.
  • the layer transfer material as described above may be contained in an amount of 20 to 40 parts by weight based on the total weight of the concrete, specifically, the total weight of the polyester resin, the filler, and optionally the following reinforcing agent. When the content of the layer transfer material is less than 20% by weight, there is a fear of deterioration of mechanical properties.
  • the layer transfer material When the content of the layer transfer material is more than 40% by weight, molding processability may be deteriorated. When it is contained within the above-mentioned content range, it is possible to exhibit an excellent mechanical property improving effect without worrying about lowering of moldability. More specifically, the layer transfer material may be contained in an amount of 20 to 30% by weight based on the total weight of the flip-chip resin, the layer transfer material, and optionally, a stiffening agent to be described later.
  • the nucleating agent acts as nuclei for crystallization during molding of the polyester resin composition, thereby improving the crystallization speed of the resin composition and improving the heat resistance and injection moldability of the polyester resin composition.
  • the inorganic nucleating agent has an excellent effect of improving the crystallization rate of the polyester resin composition, but it has a disadvantage of increasing the brittleness of the resin composition and lowering the mechanical strength.
  • the organic nucleating agent has excellent mechanical property and releasability improving effect, but the effect on the crystallization speed improvement is insignificant.
  • the present invention by using the nitride-based inorganic nucleating agent, which is more excellent in the crystallization rate improving effect, and the organic nucleating agent of the high-density polyethylene (HDPE), which are more excellent in the mechanical property and the releasing property improving effect, The speed can be improved, and at the same time the releasability and the mechanical properties can be improved.
  • the nitride-based inorganic nucleating agent which is more excellent in the crystallization rate improving effect
  • the organic nucleating agent of the high-density polyethylene (HDPE) which are more excellent in the mechanical property and the releasing property improving effect
  • a nitride-based inorganic nucleating agent having a high thermal conductivity, a high temperature stability, and an excellent crystallization speed improving effect when applied to a polyester resin composition can be used.
  • the nitride-based inorganic nucleating agent may be a non-metallic element such as boron (B) or silicon (Si); An amphoteric element such as aluminum (A1); Or a nitride including a transition metal such as titanium (Ti), tantalum (Ta), vanadium (V), chromium (Cr), molybdenum (Mo), tungsten (W) or niobium
  • boron nitride (BN), aluminum nitride (A1N), silicon nitride (Si 3 N 4), titanium nitride (TiN), tantalum nitride (TaN, Ta 2 N), nitride, vanadium (VN), chromium nitride (CrN, Cr 2 N), molybdenum nitride ( ⁇ 2 ⁇ ) may be made of niobium nitride (NbN), or tungsten nitride (
  • boron nitride-based compound having an excellent effect of improving the crystallization rate of the polyester resin composition and having excellent compatibility with high-density polyethylene can be used.
  • boron nitride is hexagonal boron nitride (Hexagonal boron nitride), cubic boron nitride, pyrolytic boron nitride (8 1 1 "01 1; ? Boron Nitride) and the like, any one or two or more common compounds of these
  • IND-11 TM manufactured by Spearman Co., Ltd.
  • the inorganic nucleating agent may be included in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the blend including the above polyester and filler, and optionally a stiffening agent to be described later. If the content of the inorganic nucleating agent is less than 0.01 parts by weight, the effect of improving the crystallization rate with the presence of the inorganic nucleating agent is insignificant. If the content is more than 2 parts by weight, the mechanical strength of the resin composition may be deteriorated. Considering the remarkable improvement effect of controlling the content of the inorganic nucleating agent, the inorganic nucleating agent is more specifically 0.1 to 1 wt% based on 100 parts by weight of the polyester and filler, and optionally, Or 0.1 to 0.5 parts by weight.
  • the organic nucleating agent a high-density poly-resin can be used. More specifically, the organic resin is excellent in improving mechanical properties and releasability due to its low adhesion with metal and its reinforcing effect, High-density polyethylene excellent in surface property improving effect in the production of a molded article can be used.
  • high-density polyethylene means polyethylene having a density of 0.92 g / cm 3 or more as measured according to ASTM D1505. Even in density control
  • the high density polyethylene is preferably a polyethylene having a density of 0.92 to 1.0 g / cm 3 , more specifically 0.95 to 1.0 g / cirf, still more specifically 0.96 to 0.98 g / cii, have. It is possible to exhibit a better mechanical property and a releasability improving effect when the above density range is satisfied. If the density of the high-density polyethylene is less than 0.92 g / cm 3 , the crystallization temperature is lowered and the effect of improving the crystallization rate can not be obtained.
  • the high-density polyethylene a product prepared by directly using a conventional polymerization reaction to meet the above-mentioned conditions may be used, or a commercially available product such as Yuzex 7200 (manufactured by SK General Chemicals) may be used.
  • the organic nucleating agent may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the blend including the polyester and the filler, and optionally a starch reinforcing agent described later.
  • the content of the fl y-olefin-based organic nucleating agent is less than 0.1 part by weight, the effect of improving the mechanical strength and releasability is insignificant.
  • the content exceeds 5 parts by weight the effect of increasing the crystallization is insignificant, The mechanical properties of the resin composition deteriorate and appearance defects occur.
  • the organic nucleating agent is more preferably used in an amount of 0.5 to 100 parts by weight based on 100 parts by weight of the polyester containing the polyester and the layer transfer agent, 3 parts by weight and black may be contained in 1 to 2 parts by weight.
  • the inorganic nucleating agent and the organic nucleating agent are mixed at a weight ratio of 1: 2 to 1:20, more specifically, May be included in a weight ratio of 1: 5 to 1:10.
  • the crystallization speed and the mechanical properties and the releasability improving effect can be improved by the use of different kinds of nucleating agent combination.
  • the polyester resin composition according to one embodiment of the present invention has the above- In order to complement or enhance the physical properties of the polyester resin composition, an impact modifier may further be included.
  • the above-mentioned weight modifier can impart toughness to the polyester resin composition to improve the tensile strength.
  • a vinylidene fluoride-diene rubber-aromatic vinyl graft copolymer examples include a vinylidene fluoride-diene rubber-aromatic vinyl graft copolymer, an alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer, an alkyl methacrylate-silicone / alkyl acrylate graft copolymer , Or an ethylene-alkyl acrylate-glycidyl methacrylate copolymer, and any one or two or more of these may be used.
  • the above-mentioned modulus reinforcing agent is more specifically an ethylene-alkyl acrylate-glycidyl methacrylate copolymer , More specifically, random terpolymers obtained by polymerizing ethylene, acrylic ester and glycidyl methacrylate under high pressure can be used.
  • Commercially available thickener reinforcements include Elvaloy (TM) PTW from DuPont.
  • the above-mentioned reinforcing agent is further included, it is preferably not more than 10% by weight, more specifically 0.1 to 10% by weight, more preferably 0.1 to 5% by weight based on the total weight of the composition including the polyester resin, the layer transfer agent and the impact modifier %. ≪ / RTI >
  • the polyester resin composition according to one embodiment of the present invention may further contain additives such as an antioxidant, a pigment, a lubricant, an antioxidant, a plasticizer, a coloring inhibitor, a matting agent, a deodorant, a flame retardant, a weathering additive, an antistatic agent, An additive such as an ultraviolet absorber, an antistatic agent,
  • the antioxidant suppresses the yellowing of the polymer resin, thereby improving the appearance of the polymer resin composition and the molded article, and inhibiting oxidation or pyrolysis.
  • examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and hindered amine-based light stabilizers.
  • a complex antioxidant containing a phenol-based antioxidant and a phosphorus-based antioxidant may be used.
  • the antioxidant may be a phenol-based first antioxidant and a second phenol-based antioxidant which are excellent in the prevention of coloring and deterioration of physical properties of a molded article due to heat or oxidation, And more specifically a phenol based low U antioxidant and a phosphorus-based second antioxidant are mixed in a weight ratio of 2: 1 to 1: 2, or 1: 1 to 1: 2, Can be used.
  • phenolic antioxidant examples include 1,3,5-trimethyl-2,4,6-tris (3,5-di-6-butyl-4-hydroxybenzyl) 3- (3,5-tert-butyl-4-hydroxybenzyl) benzene), 1,6-bis [3- (3,5- butyl-4-hydroxyphenyl) propionamido] nucleic acid (1,6-Bis [3- (3,5-di- tert- Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamido] propane (1,6- propionamido] pr opane), tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane Any one or two or more of these may be used.
  • phenolic antioxidants include ADEKA A0-60 (TM) and the like.
  • Specific examples of the phosphorus-based second antioxidant include phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethylphosphonoacetate, bis (2,6-di-tert- butyl-4-methylphenyl) pentaerythritol Bis-2,6-di-tert-butyl-4-methylphenyl pentaerythrityl to di-phosphite), bis (2,4-di-tert- butylphenyl) pentaerythritol Di- phosphite (3, 2,4- (11-161-butylphenyl) pentraerythrin tol-di-phosphite), and any one or two or more of them may be used.
  • Possible phosphorus antioxidants include S9228 TM from Doverphos, etc. If the content of antioxidant in the polyester resin composition is too high, If the above-mentioned antioxidant is further included, it is preferable to add 100 parts by weight of the polyester resin, the layer transfer agent and optionally the stiffness enhancer to the polymeric resin composition, because the mechanical properties, particularly the heat resistance, , And 10 parts by weight or less. Considering the improvement of the appearance characteristics of the polymer resin composition and the molded article due to the introduction of the antioxidant and the effect of preventing oxidation or pyrolysis without worrying about deterioration of mechanical properties,
  • the pigments include carbon black, titanium oxide, zinc oxide, zinc sulfide, zinc sulfate, barium sulfate, lithopone (li thopone, BaS0 4 ⁇ ZnS ), white lead (whi te l ead, 2PbC03 - Pb (0H) 2 ), Calcium carbonate, alumina, boron nitride, and the like, and any one or two or more of them may be used.
  • the above-mentioned pigment may be included in an amount of 10 parts by weight or less based on 100 parts by weight of the polyester resin, the layer transfer agent, and optionally, the stiffening agent. More specifically, have.
  • the lubricant can be used to stably disperse a layer transfer material, a pigment or the like in the resin composition and to easily mold the resin composition.
  • activators include metal stearate lubricants, amide lubricants, paraffin lubricants, and ester lubricants, and any one or two or more of these lubricants may be used. More specifically, N, N'-ethylene bis (stearamide) and the like can be used.
  • the above-mentioned lubricant when the above-mentioned lubricant is further included, it may be contained in an amount of 10 parts by weight or less based on 100 parts by weight of the blend including the polyester resin, the layer transfer agent, and optionally, the stiffening agent, more specifically 0.1 to 5% ≪ / RTI >
  • the polyester resin composition according to one embodiment of the present invention when considering the excellent compatibility with the polyester resin, the layer transfer agent and the nucleating agent, the stable manifestation of excellent mechanical properties, and the effect of improving the releasability , Among the above-mentioned other additives,
  • the antioxidant may include a phenol-based antioxidant and a phosphorus-based antioxidant in a weight ratio of 2: 1 to 1: 2, and black in a weight ratio of 1: 1 to 1: 2 have.
  • the types of the stiffening agent and the antioxidant are as described above.
  • the total weight of the polyester resin, the layer transfer material, and optionally the impact modifier 60 to 80% by weight of polycyclohexylenedimethylene terephthalate resin as the polyester resin, and 20 to 40% by weight of glass fibers as the filler, a nucleating agent comprising a boron nitride and 0.01 to 2 parts by weight of an organic nucleating agent, 0.92 to about l.Og / cm 3, more specifically from 0.95 to 0.98g / cm 3
  • High-density polyethylene 0.1 to 5 parts by weight of an organic nucleating agent for the inorganic nucleating agent The weight ratio of the organic nucleating agent / inorganic nucleating agent) is 5 to 10, and the impact modifier and the antioxidant, To take over and phenolic antioxidant for the first 2 Antioxidant 2 may be to a weight ratio of 2: 1 to 1.
  • the polyester resin composition according to one embodiment of the present invention having the above composition can be produced by blending the above components with the optimum content described. At this time, blending of the respective components can be performed according to a conventional method, and a blending device may be used if necessary.
  • the polyester resin composition may be prepared by incorporating a polyester resin, a filler, a nucleating agent, and optionally at least one kind of other additive into a mixer, a blender or a team blender under the above- .
  • the resins for forming the polyester resin composition may be preferably used in a dry state.
  • the polyester resin composition according to one embodiment of the present invention contains an inorganic nucleating agent having an excellent crystallization rate improving effect and an organic nucleating agent capable of improving mechanical strength and releasability in an optimal amount to improve crystallization speed, Can be improved at the same time.
  • the polyester resin composition has a crystallization temperature of not less than 245 ° C, more specifically not less than 250 ° C, and more specifically not less than 255 ° C.
  • the polyester resin composition has a cooling time of not more than 20 seconds, more specifically not more than 15 seconds, which is the shortest time during which the polyester resin composition injected into the ASTM tensile specimen mold during injection is solidified and stably separated from the mold.
  • the polyester resin composition preferably has a tensile strength as measured by D638 of not less than 1000 kg / cm 2 , more specifically not less than 1100 kg / ciif, a flexural strength of not less than 1400 kg / cu, more specifically not less than 1600 kg / cuf , And an impact strength of 90 J / m or more, more specifically 95 J / m or more as measured according to ASTM D256.
  • the crystallization temperature of the polyester resin composition can be measured using a differential scanning calorimeter (DSC). The details of the crystallization temperature are as described in Experimental Examples below.
  • An IC socket an AC component, a presser sensor, a housing, or the like.
  • the polyester resin composition is molded by various molding methods such as injection molding, extrusion molding, extrusion blow molding, extrusion blow molding or profile molding, and post-processing such as thermoforming using the same, Or a film or the like.
  • a molded article manufactured using the polyester resin composition may be provided.
  • the molded article may be subjected to various molding methods such as injection molding, extrusion molding, extrusion blow molding, injection blow molding and profile extrusion molding, and post-processing such as thermoforming using the molding method .
  • the specific shape and size of the molded article may vary depending on the application, and examples thereof may be, for example, a shape such as a sheet, a container, or a pellet.
  • the polyester resin composition according to the present invention exhibits improved crystallization speed and exhibits excellent releasability and mechanical properties. Accordingly, it can be useful for manufacturing various electric / electronic products or automobile connectors, switches, relays, jacks, IC sockets, AC parts, presser sensors, or housings that require a high crystallization speed and good releasability and mechanical properties have.
  • Polyester resin (A) polycyclohexanediyl methylene terephthalate (PCT) (intrinsic viscosity 0.65 dl / g) obtained by condensation polymerization of terephthalic acid (TPA) and 1,4-cyclohexane dimethane (CHDM)
  • PET Polyethylene terephthalate
  • TPA terephthalic acid
  • the inorganic nucleating agent (A) boron nitride (IND-11 TM, manufactured by Spear New Materials)
  • Phenolic Oxidation Stabilizer (A0-60 TM , manufactured by ADEKA)
  • PCT polycyclohexylsilane dimethylene terephthalate
  • PCT polycyclohexanediyldimethylene terephthalate
  • PET polyester resin
  • B 30% by weight of a glass fiber as a filler, and 50% by weight of a stiffener (B) , 0.2 part by weight of phosphorus based antioxidant stabilizer, 0.1 part by weight of inorganic nucleating agent (A) and 1.0 part by weight of organic nucleating agent (A) 1.0 parts by weight,
  • PCT polyvinyl alcohol
  • the pellets prepared in Examples 1 and 2 and Comparative Examples 1 to 7 were injection-molded at an injection temperature of 285 ° C using an injection machine, respectively, and the injection-molded specimens were subjected to a test at 23 ⁇ 2 ° C and 50 ⁇ 5% The conditions were adjusted under the humidity conditions, and the physical properties were measured by the following method. The results are shown in Table 1 below.
  • Crystallization temperature The crystallization temperature of the polymer was measured using a differential scanning calorimeter (DSC, DSC 8000, manufacturer: PerkinElmer). Specifically, the polymer was heated to 310 ° C, held for 5 minutes, cooled to 30 ° C, and then increased in temperature. At this time, the temperature rise rate and the fall rate were adjusted to 10 ° C / min, respectively. The crystallization temperature was defined as the crystallization temperature at the maximum point of the exothermic horn from the curve appearing while decreasing the temperature.
  • Cooling Time ASTM tensile test specimen mold solidified during molding of specimen using the above polyester resin composition, And the shortest time (injection cooling time) for stable separation was measured.
  • Comparative Example 6 in which an inorganic nucleating agent of a conventional montmethane metal salt was used in combination with a high density polyethylene type organic nucleating agent
  • Comparative Example 7 in which a low density polyethylene type organic nucleating agent was used in place of the high density polyethylene type organic nucleating agent was used in place of the nitride type inorganic nucleating agent
  • the crystallization temperature was lowered and the aging time was significantly increased as compared with Examples 1 and 2. From this, it can be confirmed that a better crystallization speed improving effect can be obtained by using a combination of a nitride-based inorganic nucleating agent and a high-density polyethylene-based organic nucleating agent.
  • Example 1 when comparing Examples 1 and 2, the polyester resin composition of Example 1, which included the stratiform enhancer at a higher inclination, showed the same level of crystallization temperature and speed as compared with Example 2, The mechanical properties including tensile strength were improved due to the increase of the modifier.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a polyester resin composition that has an improved crystallization rate and exhibits excellent releasability and mechanical properties.

Description

【명세서】  【Specification】
【발명의 명칭]  [0001]
폴리에스터 수지 조성물  Polyester resin composition
【기술분야】  TECHNICAL FIELD
관련 출원 (들)과의 상호 인용  Cross-reference with related application (s)
본 출원은 2017년 9월 22일자 한국 특허 출원 제 10-2017- 0122818호에 기초한 우선권의 이익을 주장하며， 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.  This application claims the benefit of priority based on Korean Patent Application No. 10-2017- 0122818, filed on Sep. 22, 2017, the entire contents of which are incorporated herein by reference.
본 발명은 결정화 속도가 향상되고， 우수한 이형성 및 기계적 물성을 나타내는 폴리에스터 수지 조성물에 관한 것이다.  The present invention relates to a polyester resin composition which exhibits improved crystallization speed and exhibits excellent releasability and mechanical properties.
[배경기술]  BACKGROUND ART [0002]
폴리에스터 수지는 상대적으로 우수한 기계적 강도 및 탄성 강도가 갖는 특징으로 인하여， 강화 플라스틱， 도료, 필름， 성형용 수지 또는 의복의 섬유 재료 등으로 다양하게 쓰여지고 있다.  BACKGROUND OF THE INVENTION Polyester resins are widely used as reinforcing plastics, paints, films, molding resins, or textile materials for clothing due to their relatively excellent mechanical strength and elastic strength.
다양한 폴리에스터 수지 중에서도 폴리시클로핵실렌디메틸렌 테레프탈레이트 (PCT)는 내열도와 내변색성， 내화학성 등의 특징이 매우 우수한 고내열 플라스틱 소재로서， 유리섬유 (Gl ass f i ber )와 같은 기계적 물성 보강용 충전재를 적용하여 LED 반사판， 커넥터， 식기용기， 제빵를 등의 생활용품， 전기， 전자부품 및 자동차 부품용 소재로 적용이 되고 있다. 그러나， 이러한 우수한 물성에도 불구하고， PCT 소재는 결정화 속도가 느려서， 사출 성형시 충분히 넁각되지 못할 경우 이형 불량이 발생하기 쉽다. 또 이형 불량 방지를 위해 충분한 넁각 시간을 부여할 경우， 전체 성형 사이클이 지연되는 문제가 있다. 이것은 사출성형 업체나 부품 제조업체의 생산성을 저하시킬 수 있기 때문에， PCT 소재의 다양한 용도 적용에 장애요인이 될 수 있다.  Among various polyester resins, polycyclohexanediyldimethylene terephthalate (PCT) is a high heat-resistant plastic material with excellent heat resistance, resistance to discoloration and chemical resistance, and is reinforced with mechanical properties such as glass fiber (Glass fi ber) It has been applied to household products such as LED reflector, connector, tableware container, baking, electric, electronic parts and automobile parts by applying filler. However, despite the excellent physical properties, the PCT material has a slow crystallization rate and is liable to cause defective molding when it is not sufficiently deflected during injection molding. Further, when sufficient aging time is given for prevention of mold release defects, the entire molding cycle is delayed. This can hinder the application of PCT materials to a variety of applications because it can reduce the productivity of injection molding or component manufacturers.
【발명의 상세한 설명】  DETAILED DESCRIPTION OF THE INVENTION
【기술적 과제】  [Technical Problem]
본 발명의 목적은 결정화 속도가 향상되고, 우수한 이형성 및 기계적 물성을 나타내는 폴리에스터 수지 조성물을 제공하는 것이다. 본 발명의 또 다른 목적은， 상기 폴리에스터 수지 조성물을 이용하여 제조되어， 우수한 이형성 및 기계적 물성을 나타내는 성형품을 제공하는 것이다. It is an object of the present invention to provide a polyester resin composition which exhibits improved crystallization speed and exhibits excellent releasability and mechanical properties. It is still another object of the present invention to provide a molded article produced using the polyester resin composition and exhibiting excellent releasability and mechanical properties.
【기술적 해결방법】  [Technical Solution]
상기와 같은 목적을 달성하기 위해, 본 발명자는 결정화 속도가 향상되고， 이형성 및 기계적 물성이 우수한 폴리에스터 수지 조성물에 대한 거듭된 연구 끝에 이를 제조하는데 성공하고， 제조한 폴리에스터 수지 조성물이 다양한 분야， 특히 빠른 결정화 속도와 함께 우수한 이형성 및 기계적 물성이 요구되는 각종 전기 /전자 제품 또는 자동차의 컨넥터， 스위치, 릴레이， 잭， IC 소켓， 교류부품， 프레서 센서 또는 하우징류 등에 적용가능함을 확인하여 본 발명을 완성하였다.  In order to achieve the above object, the inventor of the present invention has succeeded in manufacturing a polyester resin composition having improved crystallization speed, excellent releasability and mechanical properties, and succeeded in producing the polyester resin composition. It can be applied to a variety of electric / electronic products or automobile connectors, switches, relays, jacks, IC sockets, AC parts, presser sensors or housings which require excellent releasability and mechanical properties along with rapid crystallization speed. Completed.
이하 발명의 구체적인 구현예에 따른 폴리에스터 수지 조성물 및 이를 이용하여 제조한 성형품에 관하여 보다 상세하게 설명하기로 한다. 이에 앞서， 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며， 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.  Hereinafter, a polyester resin composition according to a specific embodiment of the present invention and a molded article produced using the same will be described in detail. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined.
따라서， 본 명세서에 기재된 실시예에 도시된 구성은 본 발명의 가장 바람직한 일 실시예에 불과할 뿐이고 본 발명의 기술적 사상에 모두 대변하는 것은 아니므로， 본 출원시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형예들이 있을 수 있음을 이해하여야 한다.  Therefore, the configurations shown in the embodiments described herein are merely the most preferred embodiments of the present invention, and are not intended to represent all of the technical ideas of the present invention, so that various equivalents And variations are possible.
본 명세서에서 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한， 복수의 표현을 포함한다. 본 명세서에서， "포함하다"， "구비하다" 또는 "가지다" 등의 용어는 실시된 특징， 슷자， 단계， 구성 요소 또는 이들을 조합한 것이 존재함을 지정하려는 것이지， 하나 또는 그 이상의 다른 특징들이나 숫자， 단계， 구성 요소， 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.  As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. In this specification, the terms " comprising, " " comprising, " or " having ", or the like, are intended to specify the presence of stated features, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.
또， 본 명세서에 있어서, "폴리에스터 "란 하나 이상의 카르복실산 (acid)과 하나 이상의 디을 (diol) 화합물과의 중축합에 의해 제조되는 합성 중합체로서， "코플리에스터 "를 포함한다. In the present specification, the term " polyester " As a synthetic polymer prepared by polycondensation of a carboxylic acid with one or more diol compounds, including " coplyester ".
또， 본 명세서에 있어서 폴리에스터 내 "반복단위"란， 카보닐옥시기를 통해 결합된 디올 유래 작용기 또는 카르복실산 유래 작용기를 갖는 단위 구조를 의미한다.  In the present specification, the term " repeating unit " in the polyester means a unit structure having a diol-derived functional group or carboxylic acid-derived functional group bonded through a carbonyloxy group.
본 발명에서는 폴리에스터 수지 및 충전재를 이용한 폴리에스터 수지 조성물의 제조시， 결정화 속도 개선 효과가 우수한 무기 핵제와， 상기 무기 핵제의 사용에 따른 수지 조성물의 기계적 특성 및 이형성을 보완할 수 있는 유기 핵제를 조합 사용함으로써， 결정화 속도를 증가시키고， 기계적 특성 및 이형성을 동시에 개선할 수 있다.  In the present invention, an inorganic nucleating agent having an excellent effect of improving the crystallization rate in the production of a polyester resin composition using a polyester resin and a filler, and an organic nucleating agent capable of compensating mechanical properties and releasability of the resin composition upon use of the inorganic nucleating agent By using the combination, the crystallization speed can be increased, and the mechanical properties and releasability can be simultaneously improved.
구체적으로， 본 발명의 일 구현예에 따른 폴리에스터 수지 조성물은， Specifically, the polyester resin composition according to one embodiment of the present invention is a polyester resin composition,
(i) 테레프탈산을 포함하는 디카르복실산 유래 반복단위와， 1,4- 사이클로핵산디메탄을을 포함하는 디올 유래 반복단위를 포함하는 폴리에스터 수지 60 내지.80중량 ¾>; 및 (ii) 충전재 20 내지 40중량 %를 포함하는 흔합물 100중량부에 대해， (i) 60 to 80 parts by weight of a polyester resin comprising a repeating unit derived from a dicarboxylic acid containing terephthalic acid and a repeating unit derived from a diol containing 1,4-cyclohexanedicarboxylic acid dimethane; And (ii) from 20 to 40% by weight of filler, based on 100 parts by weight of the blend,
(iii) 핵제로서, 질화물계 무기 핵제 0.01 내지 2중량부 및 0.92g/cm3이상의 고밀도 폴리에틸렌 (HDPE)계 유기 핵제 0.1 내지 5중량부를 포함한다. (iii) it comprises as a nucleating agent, inorganic nitride-based nucleating agent, from 0.01 to 2 parts by weight of 0.92g / cm 3 or more high-density polyethylene (HDPE) based organic nucleating agent, 0.1 to 5 parts by weight.
이하 폴리에스터 수지 조성물을 구성하는 각 성분별로 상세히 설명한다.  Hereinafter, each component constituting the polyester resin composition will be described in detail.
(i) 폴리에스터 수지  (i) Polyester resin
본 발명의 일 구현예에 따른 폴리에스터 수지 조성물에 있어서， 상기 폴리에스터 수지는 테레프탈산을 포함하는 디카르복실산계 화합물과， 1,4- 사이클로핵산디메탄을을 포함하는 디올계 화합물을 중합하여 제조한 폴리에스터 공중합체로서， 상기 테레프탈산을 포함하는 디카르복실산계 화합물 유래 반복단위와， 1,4-사이클로핵산디메탄을을 포함하는 디올계 화합물 유래 반복단위를 포함한다.  In the polyester resin composition according to one embodiment of the present invention, the polyester resin is produced by polymerizing a dicarboxylic acid-based compound containing terephthalic acid and a diol compound containing 1,4-cyclo- A repeating unit derived from a dicarboxylic acid-based compound containing the terephthalic acid and a repeating unit derived from a diol compound containing a 1,4-cyclohexanedic acid dimethane.
구체적으로， 상기 폴리에스터 수지에 있어서, 디카르복실산계 화합물 유래 반복단위는， 디카르복실산 또는 이의 에스터로부터 유래된 반복단위일 수 있다. Specifically, in the polyester resin, the repeating unit derived from a dicarboxylic acid-based compound is a repeating unit derived from a dicarboxylic acid or an ester thereof .
상기 디카르복실산은 구체적으로 탄소수 8 내지 20의 방향족 디카르복실산， 또는 탄소수 4 내지 20의 지방족 디카르복실산일 수 있으며， 보다 구체적으로 테레프탈산 (terephthalic acid; TPA), 이소프탈산 (isophthalic acid; IPA) 또는 나프탈렌 2，6-디카르복실산 (2，6- naphthalenedicarboxylic acid; 2,6-NDA) 등일 수 있다.  The dicarboxylic acid may specifically be an aromatic dicarboxylic acid having 8 to 20 carbon atoms or an aliphatic dicarboxylic acid having 4 to 20 carbon atoms. More specifically, terephthalic acid (TPA), isophthalic acid (IPA ) Or 2,6-naphthalenedicarboxylic acid (2,6-NDA).
또， 상기 디카르복실산 에스터 화합물은 탄소수 8 내지 20의 방향족 디카르복실산， 또는 탄소수 4 내지 20의 지방족 디카르복실산의 에스터일 수 있으며， 보다 구체적으로 디메틸 테레프탈레이트 (dimethyl terephthalate; DMT), 디메틸 이소프탈레이트 (dimethyl isophthalate; DMI), 또는 디메틸 2, 6-나프탈렌디카복실레이트 (dimethyl 2,6- naphthalenedicarboxylate; 2,6-NDC) 등일 수 있다.  The dicarboxylic acid ester compound may be an aromatic dicarboxylic acid having 8 to 20 carbon atoms or an ester of an aliphatic dicarboxylic acid having 4 to 20 carbon atoms. More specifically, dimethyl terephthalate (DMT) , Dimethyl isophthalate (DMI), or dimethyl 2,6-naphthalenedicarboxylate (2,6-NDC).
본 발명의 일 구현예에 따른 폴리에스터 수지 조성물에 있어서， 상기 폴리에스터 수지는 그 제조시 사용되는 디카르복실산계 화합물의 종류 및 함량을 제어함으로써， 기계적 물성， 내열성， 전기절연성 및 내층격성 면에서 보다 개선된 특성을 나타낼 수 있다.  In the polyester resin composition according to one embodiment of the present invention, the polyester resin can be produced by controlling the kind and content of the dicarboxylic acid-based compound used in the production thereof, so that the polyester resin is excellent in mechanical properties, heat resistance, And can exhibit more improved characteristics.
구체적으로， 상기 폴리에스터 수지에 있어서 디카르복실산계 화합물 유래 반복단위는， 디카르복실산계 화합물 유래 반복단위 총 몰에 대하여 테레프탈산 또는 그 에스터계 화합물 유래 반복단위를 80몰% 이상 포함할 수 있다. 이 경우， 폴리에스터 수지 조성물에 적용시 개선된 전기절연성과 함께 성형가공성을 나타내며， 또 고온 다습한 환경에서도 초기 기계적 물성을 우수한 수준으로 유지할 수 있고， 저온 성형시 우수한 결정성을 나타낼 수 있다.  Specifically, in the polyester resin, the repeating unit derived from the dicarboxylic acid-based compound may contain 80 mol% or more of repeating units derived from terephthalic acid or its ester compound based on the total moles of the repeating units derived from the dicarboxylic acid-based compound. In this case, when applied to a polyester resin composition, it exhibits improved electrical insulation and molding processability, and can maintain excellent initial mechanical properties even in a high temperature and high humidity environment, and exhibits excellent crystallinity at low temperature molding.
보다 구체적으로， 상기 폴리에스터 수지는 디카르복실산계 화합물 유래 반복단위로서 하기 화학식 1로 표시되는 반복단위를 포함할 수 있으며， 이중 80몰% 이상은 테레프탈산에서 유래한 반복단위일 수 있고， 보다 구체적으로는 하기 화학식 1에서의 Ar1이 1，4-페닐렌기인 반복단위일 수 있다: More specifically, the polyester resin may contain a repeating unit derived from a dicarboxylic acid-based compound as a repeating unit represented by the following formula (1), wherein at least 80 mol% of the repeating unit may be a repeating unit derived from terephthalic acid, as is to be Ar 1 is a 1,4-phenylene group in the repeating unit of formula I:
[화학식 1]
Figure imgf000006_0001
[Chemical Formula 1]
Figure imgf000006_0001
상기 화학식 1에서， Ar1은 치환 또는 비치환된 탄소수 6 내지 18의 아릴렌기이다. In the above formula (1), Ar 1 is a substituted or unsubstituted arylene group having 6 to 18 carbon atoms.
디카르복실산계 화합물의 종류 및 함량 제어에 따른 기계적 물성, 내열성， 전기절연성 및 내층격성 개선 효과의 현저함을 고려할 때, 상기 폴리에스터 수지에 있어서， 상기 디카르복실산계 화합물 유래 반복단위는 보다 구체적으로 디카르복실산계 화합물 유래 반복단위 총 몰에 대하여 테레프탈산 또는 그 에스터 화합물 유래 반복단위 80 내지 100몰%； 및 이소프탈산 또는 그 에스터계 화합물 유래 반복단위 0 내지 20몰 ¾>를 포함할 수 있다.  Considering the type and content control of the dicarboxylic acid compound and the remarkable effect of improving the mechanical properties, heat resistance, electrical insulation and inner layer toughness of the polyester resin, the repeating unit derived from the dicarboxylic acid- , 80 to 100 mol% of repeating units derived from terephthalic acid or its ester compound, and 0 to 20 mol% of repeating units derived from isophthalic acid or its ester compound, based on the total molar amount of the repeating units derived from the dicarboxylic acid compound.
한편， 상기 폴리에스터 수지에 있어서， 디올계 화합물 유래 반복단위는 1 , 4—사이클로핵산디메탄올 유래 반복단위를 포함할 수 있다. 상기 1，4-사이클로헥산디메탄을 유래 반복단위는 탄소수 6의 환형 구조를 포함하기 때문에 폴리카보네이트 수지와 같이 분자 쇄에 비공유 전자를 갖는 페닐렌기를 포함하는 수지에 비해 전기 절연성이 우수하며， 그 결과 이를 포함하는 폴리에스터 수지의 폴리에스터 수지 조성물에 적용시， 전기절연성을 크게 향상시킬 수 있다.  On the other hand, in the polyester resin, the repeating unit derived from a diol compound may contain repeating units derived from 1,4-cyclohexanedimethanol. Since the repeating unit derived from 1,4-cyclohexane dimethane contains a cyclic structure having 6 carbon atoms, the repeating unit derived from 1,4-cyclohexane dimethane has excellent electrical insulation as compared with a resin containing a phenylene group having non-covalent electrons in a molecular chain such as a polycarbonate resin, As a result, when applied to a polyester resin composition comprising the polyester resin, the electrical insulation can be greatly improved.
상기 1 , 4-사이클로핵산디메탄을 유래 반복단위는 폴리에스터 수지를 구성하는 디올계 화합물 유래 반복단위 총 몰에 대하여 5몰% 이상, 구체적으로는 5 내지 100몰 %， 보다 더 구체적으로는 60 내지 100몰%로 포함될 수 있다. 상기한 함량 범위로 포함될 때， 폴리에스터 수지 조성물의 우수한 기계적 물성을 유지하면서도 전기절연성 및 내열성을 크게 향상시킬 수 있다.  The repeating unit derived from the 1,4-cyclohexanedimethanemethane is present in an amount of 5 mol% or more, specifically 5 to 100 mol%, more specifically, 60 mol% or more, based on the total moles of repeating units derived from the diol compound constituting the polyester resin To 100 mol%. When included in the above-mentioned content range, electrical insulation and heat resistance can be greatly improved while maintaining excellent mechanical properties of the polyester resin composition.
또， 상기 폴리에스터 수지에 있어서 디올계 화합물 유래 반복단위는 상기한 1 , 4-사이클로핵산디메탄올 유래 반복단위와 함께， 에틸렌 글리콜， 디에틸렌 글리콜, 1 , 4-부탄디올， 1，3-프로판디을 또는 네오펜틸 글리콜 등과 같은 기타의 디을계 화합물 유래 반복단위를 1종 이상 더 포함할 수 있다. 구체적으로 상기 폴리에스터 수지는 하기 화학식 2로 표시되는 반복단위를 포함하되， 이중 하기 화학식 2에서 R1이 사이클로핵실렌디메틸렌이고， u가 0인 반복단위를， 디올계 화합물 유래 반복단위 총 몰에 대하여 5몰% 이상， 보다 구체적으로는 60 내지 100몰%로 포함하고, 이외 디올계 화합물 유래 반복단위， 이중에서도 폴리에스터 수지의 내층격성을 더욱 개선시킬 수 있는 에틸렌 -리콜 유래 반복단위- 잔부의 양으로 포함할 수 있다: In the polyester resin, the repeating unit derived from a diol compound may be a repeating unit derived from the above-mentioned 1,4-cyclohexanedimethanol-derived repeating unit, such as ethylene glycol, diethylene glycol, 1,4-butanediol, Or neopentyl glycol, and other repeating units derived from a di-based compound. Specifically, the polyester resin comprises a repeating unit represented by the following general formula (2), wherein in the general formula (2), the repeating unit in which R 1 is cyclonuclearcyclinodimethylene and u is 0 is a repeating unit derived from the repeating unit derived from the diol compound Of recurring units derived from an ethylene-based recurring unit which can further improve the inner layer intrinsic property of the polyester resin, in addition to the repeating unit derived from a diol compound, It can be included in the negative amount:
[화학식 2]  (2)
O )—-R R ^'-^YY—- R2— 0-O ) -R & lt ; 1 & gt ; R < 2 &
U U
상기 화학식 2 에서，  In Formula 2,
R1은 치환 또는 비치환된 탄소수 1 내지 10의 직쇄， 분지쇄 또는 고리형 알킬렌기이고， R 1 is a substituted or unsubstituted, linear, branched or cyclic alkylene group having 1 to 10 carbon atoms,
R2는 치환 또는 비치환된 탄소수 1 내지 10의 직쇄 또는 분지쇄 알킬렌기이며， R 2 is a substituted or unsubstituted, linear or branched alkylene group having 1 to 10 carbon atoms,
Y는 -0-， -NH- 또는 -S-이고，  Y is -O-, -NH- or -S-,
u는 0 또는 1의 정수이다.  u is an integer of 0 or 1.
보다 구체적으로， 상기 폴리에스터 수지는 테레프탈산과 1 , 4- 사이클로핵산디메탄을의 중축합에 의해 제조된 폴리사이클로핵실렌디메틸렌 테레프탈레이트 수지일 수 있으며， 상기 1 , 4-사이클로핵산디메탄올에 일부 에틸렌 글리콜이 디올계 화합물 유래 반복단위 100몰 >에 대하여 1몰% 이하의 함량으로 공중합되거나， 또는 상기 테레프탈산에 일부 이소프탈산이 디카르복실산 유래 반복단위 100몰 %에 대하여 20몰¾> 이하의 함량으로 공중합된 것일 수 있다.  More specifically, the polyester resin may be a polycycloalkanediyldimethylene terephthalate resin prepared by polycondensation of terephthalic acid and 1,4-cyclohexanedimethanemethane, and the 1,4-cyclohexanedimethanol A part of ethylene glycol is copolymerized in an amount of not more than 1 mol% based on 100 mol of a repeating unit derived from a diol compound, or a part of isophthalic acid is copolymerized with terephthalic acid in an amount of not more than 20 mol% By weight.
상기 폴리사이클로핵실렌디메틸렌 테레프탈레이트 수지는 결정화 속도가 폴리부틸렌테레프탈레이트 (PBT) 보다는 늦지만 폴리에틸렌테레프탈레이트 (PET)보다는 월등히 빠르고， 사출 성형이 가능하면서도 높은 내열성을 가지며 상대적으로 가격 경쟁력이 높아 잠재적 용도 가능성이 매우 높다. 또， 액정 폴리머를 제외하고는 현존하는 폴리에스터계 수지 중에서 가장 높은 용융점을 갖는 고분자이며， 폴리아크릴레이트 (PA)계 고분자 대비 수분 흡수율이 낮고 열에 의한 내변색성이 매우 우수하다. 이에 따라， 상기 본 발명에 따른 폴리에스터 수지 조성물이 상기 폴리에스터 수지로서 폴리사이클로핵실렌디메틸렌 테레프탈레이트 수지를 포함할 경우， 층격강도를 유지하면서도 내열성과 기계적 강도를 크게 향상시킬 수 있다. The polycyclohexanediyldimethylene terephthalate resin has a crystallization speed much faster than that of polyethylene terephthalate (PET), although it is later than polybutylene terephthalate (PBT), has high heat resistance while being injection-molding capable, and relatively high in price competitiveness Potential application possibilities are very high. Further, except for the liquid crystal polymer, it is a polymer having the highest melting point among the existing polyester resins, Has a low water absorption rate as compared with a polyacrylate (PA) type polymer and is excellent in discoloration resistance due to heat. Accordingly, when the polyester resin composition according to the present invention contains the polycyclohexanediyl methylene terephthalate resin as the polyester resin, heat resistance and mechanical strength can be greatly improved while maintaining the tensile strength.
또， 상기와 같은 폴리에스터 수지는 그 구성성분들의 종류와 함량， 그리고 중합 조건의 제어를 통해， 이형성 , 기계적 물성， 내열성， 내충격성 , 전기전연성 등의 면에서 보다 우수한 효과를 나타낼 수 있도록 점도， 중량평균 분자량 또는 유리전이온도 등을 제어할 수 있다. 구체적으로， 상기한 효과의 개선을 위해 폴리에스터 수지는 용매 0-클로로페놀 (0CP)에 용해시킨 후 35°C에서 측정한 점도로부터 환산된 고유 점도가 0.50 내지 1.2dl /g일 수 있다. 상기한 범위 내의 고유 점도를 가질 때， 적절한 분자량으로 인해 기계적 물성 저하의 우려가 없고， 또 우수한 블렌딩 효율 및 성형성을 나타낼 수 있다. 상기한 효과와 더불어 폴리에스터 수지의 고유 점도 제어에 따른 이형성 및 기계적 물성의 개선 효과에 있어서의 현저함을 고려할 때 보다 구체적으로는 0.50 dl /g 이상 0.80 dl /g미만， 보다 더 구체적으로는 0.60 내지 0.70 dl/g일 수 있다. In order to exhibit more excellent effects in terms of releasability, mechanical properties, heat resistance, impact resistance, electric conductivity and the like through control of the type and content of constituent components and polymerization conditions, Weight average molecular weight, glass transition temperature and the like can be controlled. Specifically, in order to improve the above-mentioned effect, the polyester resin may have an intrinsic viscosity of 0.50 to 1.2 dl / g converted from a viscosity measured at 35 ° C after dissolving in a solvent 0-chlorophenol (0CP). When having an intrinsic viscosity within the above-mentioned range, there is no fear of deterioration of mechanical properties due to an appropriate molecular weight, and excellent blending efficiency and moldability can be exhibited. In consideration of the remarkable effect in improving the releasability and the mechanical properties according to the intrinsic viscosity control of the polyester resin, more specifically not less than 0.50 dl / g and not more than 0.80 dl / g, more specifically not more than 0.60 dl / To 0.70 dl / g.
또， 상기 폴리에스터 수지는 상기한 고유 점도 조건을 충족하는 동시에 중량평균분자량 (Mw)이 10 , 000 내지 100 , 000 g/irol이며， 유리전이온도 (Tg)가 0 내지 200 °C , 보다 구체적으로는 80 내지 120°C인 것일 수 있다. 한편， 본 발명에 있어서, 중량평균분자량 (Mw)은 GPC(gel permeat ion chromatography)로 측정한， 표준 폴리스티렌 환산 수치를 의미하고， 유리전이온도 (Tg)는 시차주사열량계 (Di f ferent i al Scanning Calor imetry, DSC)를 이용하여 측정한 온도아다. The above-mentioned polyester resin preferably has a weight-average molecular weight (Mw) of 10,000 to 100,000 g / irol and a glass transition temperature (Tg) of 0 to 200 ° C, more specifically Lt; RTI ID = 0.0 > 120 C < / RTI > Meanwhile, in the present invention, the weight average molecular weight (Mw) means a numerical value in terms of standard polystyrene measured by gel permeation chromatography (GPC) and the glass transition temperature (Tg) is measured by a differential scanning calorimeter Calorimetry, DSC).
상기 폴리에스터 수지는， 흔합물 총 중량， 구체적으로는 폴리에스터 수지， 충전재 그리고 선택적으로 후술하는 충격보강제홑 포함하는 흔합물 총 중량에 대하여 60 내지 80중량 %로 포함될 수 있으며， 폴리에스터 수지 조성물내 폴리에스터 함량 제어에 따른 개선 효과의 우수함을 고려할 때， 60 내지 70중량 %로 포함될 수 있다. 상기한 흔합물 중 폴리에스터 수지의 함량이 60중량 % 미만이거나， 80중량 %를 초과할 경우 이형성이 저하될 우려가 있다. The polyester resin may be contained in an amount of 60 to 80% by weight based on the total weight of the concrete, specifically, the polyester resin, the filler, and optionally the total amount of the impact reinforcing agent described later, And 60 to 70% by weight, considering that the improvement effect of controlling the polyester content is excellent. Of the above-mentioned blends, When the content is less than 60% by weight or exceeds 80% by weight, the releasability may be lowered.
(ii) 층전재  (ii) layer transfer
상기 층전재는 폴리에스터 수지 조성물의 내층격성을 향상시키는 역할을 하는 것으로, 통상 폴리에스터 수지 조성물의 제조에 사용되는 것이라면 특별한 제한없이 사용가능하다. 이중에서도 발명의 일 구현예에 따른 폴리에스터 수지 조성물은 무기층전재를 포함할 수 있다.  The layer transfer material serves to improve the inner layer toughness of the polyester resin composition and can be used without any particular limitation as long as it is usually used for producing a polyester resin composition. Among them, the polyester resin composition according to one embodiment of the invention may include an inorganic layer transfer material.
상기 무기층전재의 구체적인 예로는 유리섬유， 탄소섬유， 붕소섬유, 유리비드， 유리플레이크, 탈크, 카본블랙， 클레이， 마이카， 워러스트나이트 (wollastonite), 티탄산칼슘휘스커 (calcium titanate whisker) , 붕산알루미늄휘스커 (aluminum boric acid whisker) , 산화아연휘스커 (zinc oxide whisker) , 또는 칼슘휘스커 (calcium whisker) 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다.  Specific examples of the inorganic layer transfer material include glass fiber, carbon fiber, boron fiber, glass bead, glass flake, talc, carbon black, clay, mica, wollastonite, calcium titanate whisker, aluminum borate Aluminum boric acid whisker, zinc oxide whisker, or calcium whisker. Any one or two or more of these may be used.
또, 충전재의 형태는 특별히 한정되는 것은 아니나, 층전재 사용 및 형태제어에 따른 개선 효과의 현저함을 고려할 때, 상기한 무기층전재 중에서도 유리섬유， 워러스트나이트 (wollastonite), 티탄산칼슘휘스커 (calcium titanate whisker) , 또는 붕산알루미늄휘스커 (aluminum boric acid whisker)와 같은 침상의 무기층전재가 사용될 수 있으며， 보다 구체적으로는 성형성의 향상시키고， 성형품의 인장 강도， 굽힘 강도， 굽힘 탄성률 등의 기계적 특성과 열변형 온도 등의 내열성을 향상시킬 수 있다는 점에서 유리섬유가 사용될 수 있다. 또， 상기 충전재로 유리섬유를 사용하는 경우, 필라멘트 (filament), 쓰레드 (thread), 파이버 (fiber) 또는 휘스커 (whisker) 형태의 유리섬유가 사용될 수 있다. 그리고， 상기 유리섬유는 평균 길이가 0.1 내지 20mm, 0.3 내지 10画 또는 2 내지 5隱일 수 있으며， 종횡비 (aspect ratio) ([L (섬유의 평균 길이) /D (섬유의 평균 외경) ])가 10 내지 2000， 또는 30 내지 1000일 수 있다. 상기한 종횡비 조건을 층족할 경우 보다 우수한 기계적 강도 개선 효과를 나타낼 수 있다. 상기와 같은 층전재는， 흔합물 총 중량， 구체적으로는 상기 폴리에스터 수지， 충전재 그리고 선택적으로 후술하는 층격보강제를 포함하는 흔합물 총 중량에 대하여， 20 내지 40중량 ¾>로 포함될 수 있다. 층전재의 함량이 20중량 % 미만이면 기계적 특성 저하의 우려가 있고， 40중량 %를 초과하면 성형 가공성 저하의 우려가 있다. 상기한 함량 범위 내로 포함될 때， 성형가공성 저하에 대한 우려없이 우수한 기계적 특성 개선 효과를 나타낼 수 있다. 보다 구체적으로는 상기 층전재는 플리에스터 수지, 층전재 그리고 선택적으로 후술하는 층격보강제를 포함하는 흔합물 총 중량에 대하여， 20 내지 30중량 %로 포함될 수 있다. The form of the filler is not particularly limited. However, considering the remarkable improvement effect of the use of the layer transfer material and the shape control, among the inorganic layer transfer materials, glass fiber, wollastonite, calcium titanate (calcium titanate whisker, or aluminum boric acid whisker. More specifically, it is possible to improve the moldability and to improve mechanical properties such as tensile strength, bending strength and bending elastic modulus of the molded article Glass fibers can be used in that heat resistance such as heat distortion temperature can be improved. When glass fiber is used as the filler, a glass fiber in the form of a filament, a thread, a fiber or a whisker may be used. The glass fibers may have an average length of 0.1 to 20 mm, 0.3 to 10 or 2 to 5 mm, and an aspect ratio ([L (average fiber length) / D (average fiber diameter)]) Can be from 10 to 2000, or from 30 to 1000. It is possible to exhibit an effect of improving the mechanical strength more than when the above aspect ratio conditions are satisfied. The layer transfer material as described above may be contained in an amount of 20 to 40 parts by weight based on the total weight of the concrete, specifically, the total weight of the polyester resin, the filler, and optionally the following reinforcing agent. When the content of the layer transfer material is less than 20% by weight, there is a fear of deterioration of mechanical properties. When the content of the layer transfer material is more than 40% by weight, molding processability may be deteriorated. When it is contained within the above-mentioned content range, it is possible to exhibit an excellent mechanical property improving effect without worrying about lowering of moldability. More specifically, the layer transfer material may be contained in an amount of 20 to 30% by weight based on the total weight of the flip-chip resin, the layer transfer material, and optionally, a stiffening agent to be described later.
( i i i ) 핵제  (i i) nucleating agent
일반적으로 핵제는 폴리에스터 수지 조성물의 성형 시 결정화의 핵으로 작용하여 수지 조성물의 결정화 속도를 향상시키며， 폴리에스터 수지 조성물의 내열성 및 사출성형성을 향상시키는 역할을 한다. 그 중에서도 무기 핵제의 경우 폴리에스터 수지 조성물에 대한 결정화 속도 개선 효과는 우수하나, 수지 조성물의 취성을 증가시켜 기계적 강도를 저하시키는 단점이 있다. 또， 유기 핵제의 경우 기계적 물성 및 이형성 개선 효과는 우수하나， 결정화 속도 개선에 대한 효과는 미미하다.  In general, the nucleating agent acts as nuclei for crystallization during molding of the polyester resin composition, thereby improving the crystallization speed of the resin composition and improving the heat resistance and injection moldability of the polyester resin composition. Among them, the inorganic nucleating agent has an excellent effect of improving the crystallization rate of the polyester resin composition, but it has a disadvantage of increasing the brittleness of the resin composition and lowering the mechanical strength. In addition, the organic nucleating agent has excellent mechanical property and releasability improving effect, but the effect on the crystallization speed improvement is insignificant.
이에 대해 본 발명에서는 결정화 속도 개선 효과가 보다 우수한 질화물계 무기 핵제와， 기계적 물성 및 이형성 향상 효과가 보다 우수한 고밀도 폴리에틸렌 (HDPE)의 유기 핵제를 최적 함량비로 흔합하여 사용함으로써， 폴리에스터 수지 조성물의 결정화 속도가 향상되고， 동시에 이형성 및 기계적 물성이 개선될 수 있다.  On the other hand, in the present invention, by using the nitride-based inorganic nucleating agent, which is more excellent in the crystallization rate improving effect, and the organic nucleating agent of the high-density polyethylene (HDPE), which are more excellent in the mechanical property and the releasing property improving effect, The speed can be improved, and at the same time the releasability and the mechanical properties can be improved.
구체적으로 상기 무기 핵제로는 여러 무기 핵제 중에서도 열전도도가 높고 고온에서 안정적이며， 폴리에스터 수지 조성물에 적용시 결정화 속도 개선 효과가 우수한 질화물계 무기 핵제가 사용될 수 있다. 구체적으로 상기 질화물계 무기 핵제는 붕소 (B) , 규소 (Si ) 등의 비금속 원소; 알루미늄 (A1 )과 같은 양쪽성 원소; 또는 티타늄 (Ti ) , 탄탈륨 (Ta) , 바나듐 (V) , 크롬 (Cr) , 몰리브덴 (Mo) , 텅스텐 (W) 또는 니오브 (Nb) 등과 같은 전이금속을 포함하는 질화물일 수 있으며， 보다 구체적으로는 질화붕소 (BN), 질화알루미늄 (A1N), 질화규소 (Si3N4), 질화티타늄 (TiN), 질화탄탈륨 (TaN, Ta2N) , 질화바나듐 (VN), 질화크롬 (CrN, Cr2N) , 질화몰리브덴 (Μο2Ν), 질화니오브 (NbN) 또는 질화텅스텐 (WN, W2N) 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다. Specifically, among the various inorganic nucleating agents, a nitride-based inorganic nucleating agent having a high thermal conductivity, a high temperature stability, and an excellent crystallization speed improving effect when applied to a polyester resin composition can be used. Specifically, the nitride-based inorganic nucleating agent may be a non-metallic element such as boron (B) or silicon (Si); An amphoteric element such as aluminum (A1); Or a nitride including a transition metal such as titanium (Ti), tantalum (Ta), vanadium (V), chromium (Cr), molybdenum (Mo), tungsten (W) or niobium Specifically, boron nitride (BN), aluminum nitride (A1N), silicon nitride (Si 3 N 4), titanium nitride (TiN), tantalum nitride (TaN, Ta 2 N), nitride, vanadium (VN), chromium nitride (CrN, Cr 2 N), molybdenum nitride (Μο 2 Ν), may be made of niobium nitride (NbN), or tungsten nitride (WN, W 2 N), etc., there are one or two or more of these common compounds can be used.
이중에서도 폴리에스터 수지 조성물의 결정화 속도 개선 효과가 보다 우수하고， 고밀도 폴리에틸렌과의 상용성이 우수한 질화붕소 (boron nitride)계 화합물이 사용될 수 있다. 또 상기 질화붕소로는 육방정 질화붕소 (Hexagonal boron nitride), 입방정 질화붕소, 열분해 질화붕소(?8 1 1"01 1; Boron Nitride) 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다. 또 질화붕소계 무기 핵제로는 상업적으로 입수 가능한 IND-11™ (스피아신소재사제 ) 등이 사용될 수도 있다. Among them, a boron nitride-based compound having an excellent effect of improving the crystallization rate of the polyester resin composition and having excellent compatibility with high-density polyethylene can be used. In addition to the boron nitride is hexagonal boron nitride (Hexagonal boron nitride), cubic boron nitride, pyrolytic boron nitride (8 1 1 "01 1; ? Boron Nitride) and the like, any one or two or more common compounds of these As the boron nitride-based inorganic nucleating agent, commercially available IND-11 ™ (manufactured by Spearman Co., Ltd.) and the like may be used.
상기 무기 핵제는 상기한 폴리에스터 및 충전재， 그리고 선택적으로 후술하는 층격보강제를 포함하는 흔합물 100중량부에 대하여 0.01 내지 2중량부로 포함될 수 있다. 무기 핵제의 함량이 0.01중량부 미만이면， 무기 핵제 포함에 따른 결정화 속도 개선 효과가 미미하고， 2중량부를 초과하면 오히려 수지 조성물의 기계적 강도가 저하될 우려가 있다. 무기 핵제의 함량 제어에 따른 개선 효과의 현저함을 고려할 때 상기 무기 핵제는 보다 구체적으로 상기한 폴리에스터 및 충전재， 그리고 선택적으로 후술하는 층격보강제를 포함하는 흔합물 100중량부에 대하여 0.1 내지 1중량부， 혹은 0.1 내지 0.5중량부로 포함될 수 있다.  The inorganic nucleating agent may be included in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the blend including the above polyester and filler, and optionally a stiffening agent to be described later. If the content of the inorganic nucleating agent is less than 0.01 parts by weight, the effect of improving the crystallization rate with the presence of the inorganic nucleating agent is insignificant. If the content is more than 2 parts by weight, the mechanical strength of the resin composition may be deteriorated. Considering the remarkable improvement effect of controlling the content of the inorganic nucleating agent, the inorganic nucleating agent is more specifically 0.1 to 1 wt% based on 100 parts by weight of the polyester and filler, and optionally, Or 0.1 to 0.5 parts by weight.
한편, 상기 유기 핵제로는 고밀도 폴리을레핀계 수지가 사용될 수 있으며, 보다 구체적으로는 금속과의 접착성이 낮고 층격보강 효과가 있는 특징으로 인해 기계적 물성 및 이형성 개선 효과가 우수하며， 더 나아가 수지 조성물을 이용하여 성형품의 제조시 표면 특성 개선 효과가 우수한 고밀도 폴리에틸렌이 사용될 수 있다.  On the other hand, as the organic nucleating agent, a high-density poly-resin can be used. More specifically, the organic resin is excellent in improving mechanical properties and releasability due to its low adhesion with metal and its reinforcing effect, High-density polyethylene excellent in surface property improving effect in the production of a molded article can be used.
본 발명에 있어서 고밀도 폴리에틸렌은， ASTM D1505에 따라 측정된 밀도가 0.92 g/cm3 이상인 폴리에틸렌을 의미한다. 이중에서도 밀도 제어에 따른 개선 효과의 우수함을 고려할 때 상기 고밀도 폴리에틸렌은 구체적으로 밀도가 0.92 내지 1.0 g/cm3 , 보다 구체적으로는 0.95 내지 1.0 g/cirf , 보다 더 구체적으로는 0.96 내지 0.98 g/cii의 폴리에틸렌일 수 있다. 상기한 밀도 범위를 층족할 때 보다 우수한 기계적 물성 및 이형성 개선 효과를 나타낼 수 있다. 만약 상기 고밀도 폴리에틸렌의 밀도가 0.92 g/cm3 미만일 경우， 결정화 온도가 저하되고， 결정화 속도의 개선 효과를 얻을 수 없다. In the present invention, high-density polyethylene means polyethylene having a density of 0.92 g / cm 3 or more as measured according to ASTM D1505. Even in density control The high density polyethylene is preferably a polyethylene having a density of 0.92 to 1.0 g / cm 3 , more specifically 0.95 to 1.0 g / cirf, still more specifically 0.96 to 0.98 g / cii, have. It is possible to exhibit a better mechanical property and a releasability improving effect when the above density range is satisfied. If the density of the high-density polyethylene is less than 0.92 g / cm 3 , the crystallization temperature is lowered and the effect of improving the crystallization rate can not be obtained.
상기 고밀도 폴리에틸렌으로는 통상의 중합 반웅을 이용하여 상기한 조건을 충족하도록 직접 제조한 것이 사용될 수도 있고， 또는 상업적으로 입수 가능한 Yuzex 7200™ (SK종합화학사제) 등이 사용될 수도 있다.  As the high-density polyethylene, a product prepared by directly using a conventional polymerization reaction to meet the above-mentioned conditions may be used, or a commercially available product such as Yuzex 7200 (manufactured by SK General Chemicals) may be used.
상기 유기 핵제는 상기한 폴리에스터 및 충전재， 그리고 선택적으로 후술하는 층격보강제를 포함하는 흔합물 100중량부에 대하여 0. 1 내지 5중량부로 포함될 수 있다. 플리올레핀계 유기 핵제의 함량이 0. 1중량부 미만이면， 기계적 강도 및 이형성 개선 효과가 미미하고， 5중량부를 초과하면 결정화 상승 효과가 미미하고， 폴리에스터 수지， 특히 PCT 수지와 상 분리가 발생하여 수지 조성물의 기계적 물성이 저하되고 외관 불량이 발생하게 된다. 유기 핵제의 함량 제어에 따른 개선 효과의 현저함을 고려할 때， 상기 유기 핵제는 보다 구체적으로 상기한 폴리에스터 및 층전재， 그리고 선택적으로 후술하는 층격보강제를 포함하는 흔합물 100중량부에 대하여 0.5 내지 3중량부， 흑은 1 내지 2중량부로 포함될 수 있다.  The organic nucleating agent may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the blend including the polyester and the filler, and optionally a starch reinforcing agent described later. When the content of the fl y-olefin-based organic nucleating agent is less than 0.1 part by weight, the effect of improving the mechanical strength and releasability is insignificant. When the content exceeds 5 parts by weight, the effect of increasing the crystallization is insignificant, The mechanical properties of the resin composition deteriorate and appearance defects occur. Considering the remarkable improvement effect of controlling the content of the organic nucleating agent, the organic nucleating agent is more preferably used in an amount of 0.5 to 100 parts by weight based on 100 parts by weight of the polyester containing the polyester and the layer transfer agent, 3 parts by weight and black may be contained in 1 to 2 parts by weight.
보다 구체적으로， 발명의 일 구현예에 따른 폴리에스터 수지 조성물에 있어서 상기 무기 핵제와 유기 핵제는 상기한 각각의 함량 범위를 충족하는 조건 하에서， 1 : 2 내지 1 : 20의 중량비， 보다 구체적으로는 1 : 5 내지 1 : 10의 중량비로 포함될 수 있다. 상기한 중량비로 사용될 경우， 이종의 핵제 조합 사용에 따른 결정화 속도 향상 및 기계적 물성과 이형성 개선 효과가 보다 우수할 수 있다.  More specifically, in the polyester resin composition according to one embodiment of the present invention, the inorganic nucleating agent and the organic nucleating agent are mixed at a weight ratio of 1: 2 to 1:20, more specifically, May be included in a weight ratio of 1: 5 to 1:10. When used in the above-mentioned weight ratio, the crystallization speed and the mechanical properties and the releasability improving effect can be improved by the use of different kinds of nucleating agent combination.
C iv) 기타 첨가제  C iv) Other additives
상기 일 구현예에 따른 폴리에스터 수지 조성물은， 상기한 성분들과 함께 폴리에스터 수지 조성물의 물성을 보완 또는 강화시키기 위하여 충격보강제를 더 포함할 수 있다. The polyester resin composition according to one embodiment of the present invention has the above- In order to complement or enhance the physical properties of the polyester resin composition, an impact modifier may further be included.
구체적으로， 상기 층격보강제는 폴리에스터 수지 조성물에 인성을 부여하여 인장강도를 향상시킬 수 있다. 이러한 층격보강제로는 블포화니트릴-디엔계 고무 -방향족비닐 그라프트 공중합체， 알킬메타크릴레이트-디엔계 고무 -방향족비닐 그라프트 공중합체， 알킬메타크릴레이트-실리콘 /알킬아크릴레이트 그라프트 공중합체， 또는 에틸렌-알킬아크릴레이트-글리시딜 메타크릴레이트 공중합체 등올 들 수 있으며， 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다. 이중에서도 상기한 폴리에스터 수지 조성물과의 우수한 흔화성 및 수지 조성물에 대한 인장 강도 개선 효과의 우수함을 고려할 때， 상기 층격보강제로는 보다 구체적으로 에틸렌-알킬아크릴레이트-글리시딜 메타크릴레이트 공중합체， 보다 더 구체적으로는 에틸렌， 아크릴산 에스테르 및 글리시딜 메타크릴레이트를 고압 하에서 중합한 랜덤 삼원중합체가 사용될 수 있다. 상업적으로 입수가능한 층격보강제로는 듀폰사의 Elvaloy™ PTW 등을 들 수 있다.  Specifically, the above-mentioned weight modifier can impart toughness to the polyester resin composition to improve the tensile strength. Examples of such a modifier include a vinylidene fluoride-diene rubber-aromatic vinyl graft copolymer, an alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer, an alkyl methacrylate-silicone / alkyl acrylate graft copolymer , Or an ethylene-alkyl acrylate-glycidyl methacrylate copolymer, and any one or two or more of these may be used. In consideration of the excellent wettability with the polyester resin composition and the effect of improving the tensile strength to the resin composition, the above-mentioned modulus reinforcing agent is more specifically an ethylene-alkyl acrylate-glycidyl methacrylate copolymer , More specifically, random terpolymers obtained by polymerizing ethylene, acrylic ester and glycidyl methacrylate under high pressure can be used. Commercially available thickener reinforcements include Elvaloy (TM) PTW from DuPont.
상기한 층격보강제가 더 포함될 경우， 상기 폴리에스터 수지， 층전재 및 충격보강제를 포함하는 흔합물 총 중량에 대해, 10중량 % 이하， 보다 구체적으로는 0.1 내지 10중량 보다 더 구체적으로 0.1 내지 5중량 %로 포함될 수 있다.  When the above-mentioned reinforcing agent is further included, it is preferably not more than 10% by weight, more specifically 0.1 to 10% by weight, more preferably 0.1 to 5% by weight based on the total weight of the composition including the polyester resin, the layer transfer agent and the impact modifier %. ≪ / RTI >
또 상기 일 구현예에 따른 폴리에스터 수지 조성물은， 상기 층격보강제 외에도 산화방지제， 안료， 활제， 내가수 분해제， 가소제， 착색 방지제， 무광택제， 탈취제， 난연제， 내후성첨가제， 대전방지제， 이형제， 이은 교환제, 또는 광흡수제 등과 같은 첨가제를 1종 이상 더 포함할 수 있다.  The polyester resin composition according to one embodiment of the present invention may further contain additives such as an antioxidant, a pigment, a lubricant, an antioxidant, a plasticizer, a coloring inhibitor, a matting agent, a deodorant, a flame retardant, a weathering additive, an antistatic agent, An additive such as an ultraviolet absorber, an antistatic agent,
상기 산화방지제는 고분자 수지의 황변을 억제하여 고분자 수지 조성물 및 성형품의 외관을 양호하게 하며， 산화 또는 열분해되는 것을 억제할 수 있다. 상기 산화방지제로는 페놀계 산화 방지제， 인계 산화 방지제, 황계 산화 방지제， 장애 아민계 광안정제 등이 사용될 수 있으며， 1분자 중에 페놀계의 산화 방지기와 인계의 산화 방지기를 함께 갖는 단량체를 포함하는 복합형 산화 방지제가 사용될 수도 있다. The antioxidant suppresses the yellowing of the polymer resin, thereby improving the appearance of the polymer resin composition and the molded article, and inhibiting oxidation or pyrolysis. Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and hindered amine-based light stabilizers. A complex antioxidant containing a phenol-based antioxidant and a phosphorus-based antioxidant may be used.
또， 발명의 일 구현예에 따른 폴리에스터 수지 조성물에 있어서 상기 산화방지제로는 내열성의 저하 없이 열 또는 산화에 의한 성형체의 착색이나 물성저하 방지에 우수한 페놀계의 제 1 산화방지제와 인계 제 2산화방지제의 흔합물이 사용될 수 있으며， 보다 구체적으로는 페놀계의 저 U 산화방지제와 인계 제 2산화방지제가 2:1 내지 1:2， 혹은 1:1 내지 1:2의 중량비로 흔합된 흔합물이 사용될 수 있다.  In the polyester resin composition according to one embodiment of the present invention, the antioxidant may be a phenol-based first antioxidant and a second phenol-based antioxidant which are excellent in the prevention of coloring and deterioration of physical properties of a molded article due to heat or oxidation, And more specifically a phenol based low U antioxidant and a phosphorus-based second antioxidant are mixed in a weight ratio of 2: 1 to 1: 2, or 1: 1 to 1: 2, Can be used.
상기 페놀계 게 1산화방지제로는 1,3,5-트리메틸-2，4，6-트리스(3，5- 디^6 -부틸-4-히드록시벤질)벤젠)(1，3，5-^^^11 1-2,4，6^^3(3,5-^- tert-butyl -4-hydroxybenzy 1 ) benzene ) , 1， 6-비스 [ 3- ( 3， 5-디 -t er t -부틸 -4- 하이드록시페닐)프로피온아미도]핵산 (1,6-Bis[3— (3,5— di-tert— butyl-4- hydroxyphenyl ) r o i onam i do ] hexane ) , 1,6—비스 [3_(3,5_디一 tert一부틸 _4_ 히드록시페닐)프로피온아미도]프로판 (1,6— Bis[3-(3，5-di-tert-butyl-4- hydr oxypheny 1 )propionamido]pr opane ) , 테트라키스 [메틸렌 (3， 5一디— tert— 부틸 -4-히드록시히드로시나메이트)]메탄 (tetrakis ethylene^S-di—tert- butyl— 4_hydroxyhydrocinnamate)]methane) 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다. 또 상업적으로 입수가능한 페놀계 산화방지제로는 ADEKA사의 A0-60™ 등을 들 수 있다. 또， 상기 인계 제 2산화방지제로는 구체적으로 인산， 트리메틸포스페이트， 트리에틸포스페이트， 트리페닐포스페이트， 트리에틸 포스포노 아세테이트， 비스 (2， 6-디 -tert-부틸 -4- 메틸페닐)펜타에리트리를-디 -포스파이트 (Bis(2,6-di-tert-butyl-4- methylphenyl )pentaerythr i tol-di-phosphi te) , 비스 (2,4—디— tert— 부틸페닐)펜타에리트리를—디-포스파이트( 3(2，4-(11-161 - butylphenyl )pentraerythri tol-di-phosphi te) 등을 들 수 있으며 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다. 또 상업적으로 입수가능한 인계 산화방지제로는 Doverphos사의 S9228™ 등을 들 수 있다. 폴리에스터 수지 조성물내 산화방지제 함량이 지나치게 높을 경우， 상기 고분자 수지 조성물의 기계적 물성， 특히， 내열도 등이 저하될 수 있으므로 , 상기한 산화방지제가 더 포함될 경우， 상기 폴리에스터 수지， 층전재 그리고 선택적으로 층격보강제를 포함하는 흔합물 100중량부에 대하여， 10중량부 이하로 포함될 수 있으며， 기계적 물성의 저하에 대한 우려없이 산화방지제 투입에 따른 고분자 수지 조성물 및 성형품의 외관 특성 개선 및 산화 또는 열분해 방지 효과를 고려할 때 보다 구체적으로Examples of the phenolic antioxidant include 1,3,5-trimethyl-2,4,6-tris (3,5-di-6-butyl-4-hydroxybenzyl) 3- (3,5-tert-butyl-4-hydroxybenzyl) benzene), 1,6-bis [3- (3,5- butyl-4-hydroxyphenyl) propionamido] nucleic acid (1,6-Bis [3- (3,5-di- tert- Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamido] propane (1,6- propionamido] pr opane), tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane Any one or two or more of these may be used. Commercially available phenolic antioxidants include ADEKA A0-60 (TM) and the like. Specific examples of the phosphorus-based second antioxidant include phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethylphosphonoacetate, bis (2,6-di-tert- butyl-4-methylphenyl) pentaerythritol Bis-2,6-di-tert-butyl-4-methylphenyl pentaerythrityl to di-phosphite), bis (2,4-di-tert- butylphenyl) pentaerythritol Di- phosphite (3, 2,4- (11-161-butylphenyl) pentraerythrin tol-di-phosphite), and any one or two or more of them may be used. Possible phosphorus antioxidants include S9228 ™ from Doverphos, etc. If the content of antioxidant in the polyester resin composition is too high, If the above-mentioned antioxidant is further included, it is preferable to add 100 parts by weight of the polyester resin, the layer transfer agent and optionally the stiffness enhancer to the polymeric resin composition, because the mechanical properties, particularly the heat resistance, , And 10 parts by weight or less. Considering the improvement of the appearance characteristics of the polymer resin composition and the molded article due to the introduction of the antioxidant and the effect of preventing oxidation or pyrolysis without worrying about deterioration of mechanical properties,
0.01 내지 5중량부, 혹은 0. 1 내지 1중량부, 혹은 0. 1 내지 0.5중량부로 포함될 수 있다. 0.01 to 5 parts by weight, or 0.1 to 1 part by weight, or 0.1 to 0.5 part by weight.
또， 상기 안료로는 카본 블랙， 산화티타늄， 산화아연， 황화아연, 황산아연， 황산바륨， 리토폰 ( l i thopone , BaS04 · ZnS) , 연백 (whi te l ead , 2PbC03 - Pb(0H)2) , 탄산칼슘, 알루미나， 보론나이트라이드 (boron ni tr ide) 등을 들 수 있으며， 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다. 상기한 안료가 더 포함될 경우， 상기 폴리에스터 수지， 층전재, 그리고 선택적으로 층격보강제를 포함하는 흔합물 100중량부에 대하여 10중량부 이하로 포함될 수 있으며， 보다 구체적으로 0.01 내자 5중량부로 포함될 수 있다. In addition, the pigments include carbon black, titanium oxide, zinc oxide, zinc sulfide, zinc sulfate, barium sulfate, lithopone (li thopone, BaS0 4 · ZnS ), white lead (whi te l ead, 2PbC03 - Pb (0H) 2 ), Calcium carbonate, alumina, boron nitride, and the like, and any one or two or more of them may be used. When the above-mentioned pigment is further included, it may be included in an amount of 10 parts by weight or less based on 100 parts by weight of the polyester resin, the layer transfer agent, and optionally, the stiffening agent. More specifically, have.
또， 상기 활제는 층전재 또는 안료 등이 수지 조성물 내에 안정적으로 분산되고， 수지 조성물의 용이한 이형을 위하여 사용될 수 있다. 이러한 활제로는 금속 스테아레이트계 활제， 아마이드계 활제， 파라핀계 활제, 또는 에스터계 활제 등을 들 수 있으며， 이들 중 어느 하나 또는 둘 이상의 흔합물이 사용될 수 있다. 보다 구체적으로는 Ν , Ν ' - 에틸렌비스 (스테아르아미드) 등이 사용될 수 있다. 상기한 활제가 더 포함될 경우, 상기 폴리에스터 수지， 층전재， 그리고 선택적으로 층격보강제를 포함하는 흔합물 100중량부에 대하여 10중량부 이하로 포함될 수 있으며， 보다 구체적으로 0. 1 내지 5중량 %로 포함될 수 있다.  In addition, the lubricant can be used to stably disperse a layer transfer material, a pigment or the like in the resin composition and to easily mold the resin composition. Examples of such activators include metal stearate lubricants, amide lubricants, paraffin lubricants, and ester lubricants, and any one or two or more of these lubricants may be used. More specifically, N, N'-ethylene bis (stearamide) and the like can be used. When the above-mentioned lubricant is further included, it may be contained in an amount of 10 parts by weight or less based on 100 parts by weight of the blend including the polyester resin, the layer transfer agent, and optionally, the stiffening agent, more specifically 0.1 to 5% ≪ / RTI >
보다 구체적으로， 상기 발명의 일 구현예에 따른 폴리에스터 수지 조성물은， 상기한 폴리에스터 수지， 층전재 그리고 핵제와의 우수한 흔화성과 함께， 우수한 기계적 물성의 안정적인 발현， 그리고 이형성 개선 효과를 고려할 때， 상기한 기타 첨가제 중에서도 층격보강제 및 산화방지제를 더 포함할 수 있으며， 이때 상기 산화방지제는 페놀계 게 1산화방지제와 인계 제 2산화방지제를 2:1 내지 1:2, 흑은 1:1 내지 1:2의 중량비로 포함할 수 있다. 이때 상기 층격보강제 및 산화방지제의 종류는 앞서 설명한 바와 같다. More specifically, the polyester resin composition according to one embodiment of the present invention, when considering the excellent compatibility with the polyester resin, the layer transfer agent and the nucleating agent, the stable manifestation of excellent mechanical properties, and the effect of improving the releasability , Among the above-mentioned other additives, The antioxidant may include a phenol-based antioxidant and a phosphorus-based antioxidant in a weight ratio of 2: 1 to 1: 2, and black in a weight ratio of 1: 1 to 1: 2 have. At this time, the types of the stiffening agent and the antioxidant are as described above.
또한 상기 일 구현예에 따른 폴리에스터 수지 조성물은 구성성분과 함께 함량의 최적화에 따른 개선효과의 현저함을 고려할 때， 상기 폴리에스터 수지， 층전재， 그리고 선택적으로 충격 보강제를 포함하는 흔합물 총 중량에 대하여， 상기 폴리에스터 수지로서 폴리사이클로헥실렌디메틸렌 테레프탈레이트 수지 60 내지 80중량 %， 및 상기 충전재로서 유리섬유 20 내지 40중량 %를 포함하고， 또 상기 흔합물 100중량부에 대하여 보론계 무기 핵제로서 질화붕소 0.01 내지 2중량부 및 유기 핵제로서 0.92 내지 l.Og/cm3, 보다 구체적으로는 0.95 내지 0.98g/cm3 고밀도 폴리에틸렌 0.1 내지 5중량부를 포함하되， 상기 무기 핵제에 대한 유기 핵제의 중량비 유기 핵게 /무기 핵제)가 5 내지 10이고, 상기 충격보강제 및 산화방지제를 더 포함하며， 상기 산화방지제는 페놀계 제 1산화방지제와 인계 게 2산화방지제를 2:1 내지 1:2의 중량비로 포함하는 것일 수 있다. Also, considering the remarkable improvement effect of the polyester resin composition according to the present invention along with the optimization of the content, the total weight of the polyester resin, the layer transfer material, and optionally the impact modifier , 60 to 80% by weight of polycyclohexylenedimethylene terephthalate resin as the polyester resin, and 20 to 40% by weight of glass fibers as the filler, a nucleating agent comprising a boron nitride and 0.01 to 2 parts by weight of an organic nucleating agent, 0.92 to about l.Og / cm 3, more specifically from 0.95 to 0.98g / cm 3 High-density polyethylene 0.1 to 5 parts by weight of an organic nucleating agent for the inorganic nucleating agent The weight ratio of the organic nucleating agent / inorganic nucleating agent) is 5 to 10, and the impact modifier and the antioxidant, To take over and phenolic antioxidant for the first 2 Antioxidant 2 may be to a weight ratio of 2: 1 to 1.
보다 구체적으로， 상기 일 구현예에 따른 폴리에스터 수지 조성물은， 상기 폴리에스터 수지， 층전재 및 층격 보강제를 포함하는 흔합물 총 중량에 대하여， 상기 폴리에스터 수지로서 폴리사이클로핵실렌디메틸렌 테레프탈레이트 수지 60 내지 70중량 ¾>， 상기 층전재로서 유리섬유 20 내지 30중량 %， 그리고 충격보강제， 구체적으로는 에틸렌-알킬아크릴레이트- 글리시딜 메타크릴레이트 공중합체 0.1 내지 10중량 %를 포함하고， 상기 폴리에스터 수지， 충전재 및 층격 보강제를 포함하는 흔합물 100중량부에 대해 보론계 무기 핵제 0.01 내지 2.0중량부 및 유기 핵제로서 0.92 내지 l.Og/cm3, 보다 구체적으로는 0.95 내지 0.98g/cm3 고밀도 폴리에틸렌 0.1 내지 5중량부를 포함하되， 상기 무기 핵제에 대한 유기 핵제의 중량비 (=유기 핵제 /무기 핵제)가 5 내지 10이고, 또， 페놀계 제 1산화방지제와 인계 제 2산화방지제를 2:1 내지 1:2의 중량비로 포함하는 산화방지제를 더 포함하는 것일 수 있다. More specifically, the polyester resin composition according to one embodiment comprises, as the polyester resin, a polycyclohexanediyldimethylene terephthalate resin as the polyester resin, based on the total weight of the polyester resin, the layer transfer material, And 20 to 30% by weight of glass fiber as the layer transfer material, and 0.1 to 10% by weight of an impact modifier, specifically an ethylene-alkyl acrylate-glycidyl methacrylate copolymer, 0.01 to 2.0 parts by weight of a boron-based inorganic nucleating agent relative to 100 parts by weight of a blend including a polyester resin, a filler and a modifier, and 0.92 to 1.0 g / cm 3 as an organic nucleating agent, more specifically 0.95 to 0.98 g / cm 3 3 comprising a high density polyethylene, 0.1 to 5 parts by weight, the weight ratio of the organic nucleating agent (nucleating agent = organic / inorganic nucleating agent) of the inorganic nucleating agent is 5 By 10 and, again, the first phenolic antioxidants and phosphorus-2 Antioxidant 2: at a weight ratio of 2: 1 to 1 It may further comprise an antioxidant.
상기한 조성을 갖는 본 발명의 일 구현예에 따른 폴리에스터 수지 조성물은， 상기 구성성분들을 기재된 최적 함량으로 블렌딩함으로써 제조될 수 있다. 이때， 각 성분들의 블렌딩은 통상적인 방법에 따라 수행될 수 있으며, 필요한 경우 블렌딩 장치가 이용될 수도 있다.  The polyester resin composition according to one embodiment of the present invention having the above composition can be produced by blending the above components with the optimum content described. At this time, blending of the respective components can be performed according to a conventional method, and a blending device may be used if necessary.
구체적으로는， 상기 폴리에스터 수지 조성물은 폴리에스터 수지 , 충전재, 핵제 그리고 선택적으로 1종 이상의 기타 첨가제를 흔합기， 믹서기 또는 팀블러 등에 상기한 함량 조건으로 각각 넣은 후， 이축압출기를 통해 흔합함으로써 제조될 수 있다. 이때， 상기 플리에스터 수지 조성물 형성용 수지들은 층분히 건조된 상태에서 사용되는 것이 바람직할 수 있다.  Specifically, the polyester resin composition may be prepared by incorporating a polyester resin, a filler, a nucleating agent, and optionally at least one kind of other additive into a mixer, a blender or a team blender under the above- . At this time, the resins for forming the polyester resin composition may be preferably used in a dry state.
본 발명의 일 구현예에 따른 폴리에스터 수지 조성물은, 우수한 결정화 속도 개선 효과를 갖는 무기 핵제와， 기계적 강도 및 이형성을 향상시킬 수 있는 유기 핵제를 최적 함량으로 포함함으로써， 결정화 속도와 기계적 강도 및 이형성을 동시에 개선시킬 수 있다.  The polyester resin composition according to one embodiment of the present invention contains an inorganic nucleating agent having an excellent crystallization rate improving effect and an organic nucleating agent capable of improving mechanical strength and releasability in an optimal amount to improve crystallization speed, Can be improved at the same time.
구체적으로， 상기 폴리에스터 수지 조성물은 결정화 온도가 245 °C 이상， 보다 구체적으로는 250 °C 이상， 보다 더 구체적으로는 255 °C 이상이다. 또， 상기 폴리에스터 수지 조성물은 사출 공정시 ASTM 인장 시편 금형에 사출된 폴리에스터 수지 조성물이 고화되어 금형으로부터 안정적으로 분리되는 최단 시간인 냉각시간이 20초 이하， 보다 구체적으로 15초 이하이다. 또， 상기 폴리에스터 수지 조성물은 D638에 의해 측정한 인장강도가 1000 kg/ cm2 이상， 보다 구체적으로는 1100kg/ciif 이상이고， 굴곡강도가 1400kg/cu 이상, 보다 구체적으로는 1600kg/cuf 이상이며， ASTM D256에 의거하여 측정한 충격강도가 90 J/m 이상， 보다 구체적으로는 95 J/m 이상으로 우수한 기계적 특성을 갖는다. Specifically, the polyester resin composition has a crystallization temperature of not less than 245 ° C, more specifically not less than 250 ° C, and more specifically not less than 255 ° C. The polyester resin composition has a cooling time of not more than 20 seconds, more specifically not more than 15 seconds, which is the shortest time during which the polyester resin composition injected into the ASTM tensile specimen mold during injection is solidified and stably separated from the mold. The polyester resin composition preferably has a tensile strength as measured by D638 of not less than 1000 kg / cm 2 , more specifically not less than 1100 kg / ciif, a flexural strength of not less than 1400 kg / cu, more specifically not less than 1600 kg / cuf , And an impact strength of 90 J / m or more, more specifically 95 J / m or more as measured according to ASTM D256.
한편， 상기 폴리에스터 수지 조성물의 결정화 온도는 시차주사열량계 (Di f ferent i al Scanning Calor imeter , DSC)를 이용하여 측정할 수 있으며, 구체적으로는 그 상세는 이하 실험예에 기재된 바와 같다.  On the other hand, the crystallization temperature of the polyester resin composition can be measured using a differential scanning calorimeter (DSC). The details of the crystallization temperature are as described in Experimental Examples below.
이에 따라 빠른 결정화 속도와 함께 우수한 이형성 및 기계적 물성이 요구되는 각종 전기 /전자 제품 또는 자동차의 컨넥터， 스위치， 릴레이， 잭，As a result, excellent crystallinity and excellent releasability and mechanical properties Various electrical / electronic products or automobile connectors, switches, relays, jacks,
IC 소켓， 교류부품， 프레서 센서 또는 하우징류 등의 제조에 유용할 수 있다. An IC socket, an AC component, a presser sensor, a housing, or the like.
구체적으로， 상기 폴리에스터 수지 조성물은 다양한 성형 방법， 예를 들어 사출, 압출， 압출 블로우， 사출 블로우 또는 프로파일 압출 등의 성형공정 및 이를 이용한 열성형 공정과 같은 후가공 등의 방법을 통하여 성형함으로써, 펠렛 또는 필름 등의 형태로 구현될 수 있다.  Specifically, the polyester resin composition is molded by various molding methods such as injection molding, extrusion molding, extrusion blow molding, extrusion blow molding or profile molding, and post-processing such as thermoforming using the same, Or a film or the like.
이에 따라 본 발명의 다른 일 구현예에 따르면， 상기 폴리에스터 수지 조성물을 이용하여 제조한 성형품이 제공될 수 있다.  Accordingly, according to another embodiment of the present invention, a molded article manufactured using the polyester resin composition may be provided.
상기 성형품은 그 적용 용도에 따라서 상기 폴리에스터 수지 조성물을 다양한 성형 방법， 예를 들어 사출， 압출， 압출 블로우， 사출 블로우 및 프로파일 압출 등의 성형공정 및 이를 이용한 열성형 공정과 같은 후가공 등의 방법을 통하여 성형 함으로서 얻을 수 있다.  The molded article may be subjected to various molding methods such as injection molding, extrusion molding, extrusion blow molding, injection blow molding and profile extrusion molding, and post-processing such as thermoforming using the molding method .
또， 상기 성형품의 구체적인 형상이나 크기는 그 적용 용도에 따라 다양할 수 있으며， 그 예가 크게 한정되는 것은 아니나， 예를 들어 시트， 용기 또는 펠렛 등의 형상을 가질 수 있다.  The specific shape and size of the molded article may vary depending on the application, and examples thereof may be, for example, a shape such as a sheet, a container, or a pellet.
【발명의 효과】  【Effects of the Invention】
본 발명에 따른 폴리에스터 수지 조성물은 결정화 속도가 향상되고， 우수한 이형성 및 기계적 물성을 나타낸다. 이에 따라 빠른 결정화 속도와 함께 우수한 이형성 및 기계적 물성이 요구되는 각종 전기 /전자 제품 또는 자동차의 컨넥터， 스위치, 릴레이， 잭， IC 소켓， 교류부품， 프레서 센서 또는 하우징류 등의 제조에 유용할 수 있다.  The polyester resin composition according to the present invention exhibits improved crystallization speed and exhibits excellent releasability and mechanical properties. Accordingly, it can be useful for manufacturing various electric / electronic products or automobile connectors, switches, relays, jacks, IC sockets, AC parts, presser sensors, or housings that require a high crystallization speed and good releasability and mechanical properties have.
【발명의 실시를 위한 최선의 형태】  BEST MODE FOR CARRYING OUT THE INVENTION
이하, 발명의 구체적인 실시예를 통해， 발명의 작용 및 효과를 보다 상술하기로 한다. 다만， 이러한 실시예는 발명의 예시로 제시된 것에 불과하며， 이에 의해 발명의 권리범위가 정해지는 것은 아니다.  Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.
<폴리에스터 수지 조성물의 제조 >  &Lt; Production of polyester resin composition >
이하 실시예 및 비교예에 따른 수지 조성물의 제조시 사용한 각 화합물은하기와 같다: 폴리에스터 수지 (A): 테레프탈산 (TPA) 및 1,4- 사이클로핵산디메탄을 (CHDM)를 축합중합한 폴리시클로핵실렌디메틸렌 테레프탈레이트 (PCT) (고유점도 0.65 dl/g) Each compound used in the preparation of the resin composition according to the examples and comparative examples is as follows: Polyester resin (A): polycyclohexanediyl methylene terephthalate (PCT) (intrinsic viscosity 0.65 dl / g) obtained by condensation polymerization of terephthalic acid (TPA) and 1,4-cyclohexane dimethane (CHDM)
폴리에스터 수지 (B): 에틸렌글리콜 (EG) 및 테레프탈산 (TPA)을 축합중합한 폴리에틸렌 테레프탈레이트 (PET) (고유점도 0.8 dl/g)  Polyester resin (B): Polyethylene terephthalate (PET) (intrinsic viscosity of 0.8 dl / g) obtained by condensation polymerization of ethylene glycol (EG) and terephthalic acid (TPA)
층전재: 유리섬유 (T-187HTM, NEG사제， 섬유의 평균 길이 =3.0 ±1.0画， 섬유의 평균 외경 =10.5±1.0 m) Layer transfer: glass fiber (T-187H TM , manufactured by NIP, average length of fiber = 3.0 ± 1.0, average fiber diameter of 10.5 ± 1.0 m)
무기 핵제 (A): 질화붕소 (IND-11™, 스피어신소재사제)  The inorganic nucleating agent (A): boron nitride (IND-11 ™, manufactured by Spear New Materials)
무기 핵제 (B): 몬탄산의 나트륨염 (Licomont NaVlOl, Clariant사제 ) 유기 핵제 (A): 고밀도 폴리에틸렌 (HDPEKYuzex 7200™, (B): Sodium salt of montanic acid (Licomont NaVlOl, manufactured by Clariant) Organic nucleating agent (A): High density polyethylene (HDPEKYuzex 7200 ™,
SK종합화학사제) (ASTM D1505에 따라 측정된 밀도 0.968g/cm3) (A density of 0.968 g / cm &lt; 3 &gt; measured according to ASTM D1505)
유기 핵제 (B): 저밀도 폴리에틸렌 (LDPE) (ASTM D1505에 따라 측정된 밀도 0.915g/cm3) Organic nucleating agent (B): low density polyethylene (LDPE) (density measured according to ASTM D1505 0.915g / cm 3)
제 1 산화안정제: 페놀계 산화안정제 (A0-60TM, ADEKA사제) First Oxidation Stabilizer: Phenolic Oxidation Stabilizer (A0-60 TM , manufactured by ADEKA)
제 2 산화안정제: 인계 산화안정제 (S9228™, Doverphos사제) 층격보강제: 에틸렌 -n-부틸 아크릴레이트-글리시딜 메타크릴레이트 (E/nBA/GMA) 공중합체 (Elvaloy™ PTW, 듀폰사제)  Ethylene-n-butyl acrylate-glycidyl methacrylate (E / nBA / GMA) copolymer (Elvaloy (TM) PTW, manufactured by DuPont)
<폴리에스터 수지 조성물의 제조 > &Lt; Production of polyester resin composition >
실시예 1  Example 1
플리에스터 수지 (A)로서 폴리시클로핵실렌디메틸렌 테레프탈레이트 (PCT) 67 중량 %， 충전재로서 유리섬유 30 중량 %， 및 충격보강제 3 중량 ¾로 이루어진 흔합물 100중량부에 대해, 페놀계 게 1 산화안정제 0.2 중량부， 인계 제 2 산화안정제 0.2 중량부， 무기 핵제 (A) 0.1 중량부， 및 유기 핵제 (A) 1.0 중량부를 이축흔련압출기 (Φ: 40隱， L/D = 44)를 사용하여 균일하게 흔련 압출하여 폴리에스터 수지 조성물의 펠렛을 제조하였다. 실시예 2  Based on 100 parts by weight of a mixture composed of 67% by weight of polycyclohexylsilane dimethylene terephthalate (PCT) as the fliester resin (A), 30% by weight of glass fiber as a filler and 3% by weight of an impact modifier, (Φ: 40 , L / D = 44) was used as a polymerization initiator, 0.2 part by weight of an oxidative stabilizer, 0.2 part by weight of a phosphorus-based second oxidative stabilizer, 0.1 part by weight of an inorganic nucleating agent (A) And uniformly extruded to produce a pellet of a polyester resin composition. Example 2
폴리에스터 수지 (A)로서 폴리시클로핵실렌디메틸렌 테레프탈레이트 (PCT) 69 중량 ¾», 층전재로서 유리섬유 30 중량 %， 및 층격보강제 1.0 중량 %로 이루어진 흔합물 100중량부에 대해， 페놀계 게 1 산화안정제 0.2 중량부， 인계 제 2 산화안정제 0.2 중량부， 무기 핵제 (A) 0. 1 중량부， 유기 핵제 (A) 2.0 중량부를 이축흔련압출기 ( Φ : 40mm , L/D = 44)를 사용하여 균일하게 흔련 압출하여 폴리에스터 수지 조성물의 펠렛을 제조하였다. 비교예 1 As the polyester resin (A), polycyclohexanediyldimethylene terephthalate (PCT) 69 parts by weight, glass fiber 30 parts by weight as a layer transfer material, and 1.0 parts by weight of a stiffening agent 1.0 part by weight, 0.2 parts by weight of a phenol based antioxidant stabilizer, 0.2 parts by weight of a phosphorus- , 0.1 part by weight of the inorganic nucleating agent (A) and 2.0 parts by weight of the organic nucleating agent (A) were uniformly squeezed out using a twin screw extruder (Φ: 40 mm, L / D = 44) to prepare a pellet of the polyester resin composition . Comparative Example 1
폴리에스터 수지 (A)로서 플리시클로핵실렌디메틸렌 테레프탈레이트 (PCT) 67 중량 %， 충전재로서 유리섬유 30 중량 % 및 충격보강제 3 중량 %를 포함하는 흔합물 100중량부에 대해， 페놀계 제 1 산화안정제 0.2 중량부， 인계 제 2 산화안정제 0.2 중량부를 이축흔련압출기 ( Φ : 40mm , L/D = 44)를 사용하여 균일하게 흔련 압출하여 폴리에스터 수지 조성물의 펠렛을 제조하였다. 비교예 2  Based on 100 parts by weight of a blend containing 67% by weight of a polycyclohexenylsilylene dimethylene terephthalate (PCT) as a polyester resin (A), 30% by weight of a glass fiber as a filler and 3% by weight of an impact modifier, 0.2 part by weight of the oxidative stabilizer and 0.2 part by weight of the phosphorus-based second stabilizer were uniformly extruded by using a twin screw extruder (?: 40 mm, L / D = 44) to prepare a polyester resin composition pellet. Comparative Example 2
폴리에스터 수지 (A)로서 플리시클로핵실렌디메틸렌 테레프탈레이트 (PCT) 67 중량 ¾， 층전채로서 유리섬유 30 중량 ¾ 및 층격보강제 3 중량 %를 포함하는 흔합물 100중량부에 대해 페놀계 게 1 산화안정제 0.2 중량부， 인계 계 2 산화안정제 0.2 중량부， 및 유기 핵제 (A) 2.0 중량부를 이축흔련압출기 ( Φ : 40隱, L/D = 44)를 사용하여 균일하게 흔련 압출하여 폴리에스터 수지 조성물의 펠렛을 제조하였다. 비교예 3  100 parts by weight of a blend containing 67 wt% of a floc cyclohexanediyl methylene terephthalate (PCT) as a polyester resin (A), 30 wt% of a glass fiber as a layer base and 3 wt% of a reinforcing agent as a layer reinforcing agent, 0.2 part by weight of an oxidative stabilizer, 0.2 part by weight of a phosphorus based antioxidant stabilizer and 2.0 parts by weight of an organic nucleating agent (A) were homogeneously squeezed out by using a twin screw extruder (Φ: 40 mm, L / D = 44) A pellet of the composition was prepared. Comparative Example 3
폴리에스터 수지 (A)로서 폴리시클로핵실렌디메틸렌 테레프탈레이트 (PCT) 67 중량 %， 충전재로서 유리섬유 30 증량 % 및 충격보강제 3 중량 %를 포함하는 흔합물 100중량부에 대해, 페놀계 계 1 산화안정제 0.2 중량부， 인계 제 2 산화안정제 0.2 중량부， 및 무기 핵제 (A) 0.5 중량부를 이축흔련압출기 ( Φ : 40mm, L/D = 44)를 사용하여 균일하게 흔련 압출하여 폴리에스터 수지 조성물의 펠렛을 제조하였다. 비교예 4 Based on 100 parts by weight of a blend containing 67% by weight of polycyclohexylsilylene dimethylene terephthalate (PCT) as a polyester resin (A), 30% by weight of glass fibers as fillers and 3% by weight of an impact modifier, 0.2 parts by weight of an oxidative stabilizer, 0.2 part by weight of a phosphorus-containing second oxidative stabilizer and 0.5 parts by weight of an inorganic nucleating agent (A) were uniformly extruded by using a twin screw extruder (Φ: 40 mm, L / D = 44) Of pellets were prepared. Comparative Example 4
폴리에스터 수지 (A)로서 폴리시클로핵실렌디메틸렌 테레프탈레이트 (PCT) 57 중량 %， 폴리에스터 수지 (B)로서 폴리에틸렌테레프탈레이트 (PET) 10 중량 %， 충진재로서 유리섬유 30 중량 %， 및 층격보강제 3중량 %를 포함하는 흔합물 100중량부에 대해， 페놀계 제 1 산화안정제 0.2 중량부， 인계 계 2 산화안정제 0.2 중량부， 무기 핵제 (A) 0. 1 중량부 및 유기 핵제 (A) 1.0 중량부를 이축흔련압출기 ( Φ : 40mm, L/D = 44)를 사용하여 균일하게 흔련 압출하여 폴리에스터 수지 조성물의 펠렛을 제조하였다. 비교예 5  (PET) as a polyester resin (B), 30% by weight of a glass fiber as a filler, and 50% by weight of a stiffener (B) , 0.2 part by weight of phosphorus based antioxidant stabilizer, 0.1 part by weight of inorganic nucleating agent (A) and 1.0 part by weight of organic nucleating agent (A) 1.0 parts by weight, By weight were uniformly extruded by using a twin screw extruder (?: 40 mm, L / D = 44) to prepare pellets of a polyester resin composition. Comparative Example 5
폴리에스터 수지 (A)로서 폴리시클로핵실렌디메틸렌 테레프탈레이트 (PCT) 67 중량 %， 충전재로서 유리섬유 30 증량 % 및 층격보강제 3 중량 %를 포함하는 흔합물 100중량부에 대해， 페놀계 제 1 산화안정제 0.2 중량부， 인계 제 2 산화안정제 0.2 중량부, 무기 핵제 (A) 0. 1 중량부 및 유기 핵제 (A) 6.0 중량부를 이축흔련압출기 ( Φ : 40mm , L/D = 44)를 사용하여 균일하게 흔련 압출하여 폴리에스터 수지 조성물의 펠렛을 제조하였다. 비교예 6  Based on 100 parts by weight of a blend containing 67% by weight of polycyclohexylsilylene dimethylene terephthalate (PCT) as a polyester resin (A), 30% by weight of glass fibers as fillers and 3% by weight of a reinforcing agent as a filler, (Φ: 40 mm, L / D = 44) was used in an amount of 0.2 part by weight, an oxidizing stabilizer (0.2 part by weight), a phosphorus-based second oxidizing stabilizer (0.2 parts by weight), an inorganic nucleating agent (A) And uniformly extruded to produce a pellet of a polyester resin composition. Comparative Example 6
폴리에스터 수지 (A)로서 폴리시클로핵실렌디메틸렌 테레프탈레이트 (PCT) 67 중량 충전재로서 유리섬유 30 중량 ¾>， 및 층격보강제 3 중량 %로 이루어진 흔합물 100중량부에 대해， 페놀계 제 1 산화안정제 0.2 중량부， 인계 제 2 산화안정제 0.2 중량부， 무기 핵제 (B) 0. 1 중량부， 및 유기 핵제 (A) 1 .0 중량부를 이축흔련압출기 ( Φ : 40mm , L/D = 44)를 사용하여 균일하게 흔련 압출하여 폴리에스터 수지 조성물의 펠렛을 제조하였다. 비교예 7  Based on 100 parts by weight of a mixture consisting of 30 parts by weight of glass fiber as a filler and 67 parts by weight of polycyclohexylsilylene dimethylene terephthalate (PCT) as a polyester resin (A) and 3 parts by weight of a stiffening agent, (Φ: 40 mm, L / D = 44), 0.2 part by weight of a stabilizer, 0.2 part by weight of a phosphorus-based second oxidizing stabilizer, 0.1 part by weight of an inorganic nucleating agent (B) and 1.0 part by weight of an organic nucleating agent (A) To give pellets of a polyester resin composition. Comparative Example 7
폴리에스터 수지 (A)로서 폴리시클로핵실렌디메틸렌 테레프탈레이트 (PCT) 67 중량 %， 층전재로서 유리섬유 30 중량 및 층격보강제 3 중량 %로 이루어진 흔합물 100중량부에 대해， 페놀계 제 1 산화안정제 0.2 중량부， 인계 제 2 산화안정제 0.2 중량부， 무기 핵제 (A) 0.1 중량부， 및 유기 핵제 (B) 1.0 중량부를 이축흔련압출기 (Φ: 40mm, L/D = 44)를 사용하여 균일하게 흔련 압출하여 폴리에스터 수지 조성물의 펠렛을 제조하였다. As the polyester resin (A), polycyclohexanediyldimethylene terephthalate , 0.2 part by weight of a phenol-based first oxidative stabilizer, 0.2 part by weight of a phosphorus-based second oxidative stabilizer, and 0.1 part by weight of a phosphorus-based stabilizer were added to 100 parts by weight of a blend consisting of 67% by weight of polyvinyl alcohol (PCT) 0.1 part by weight of the nucleating agent (A) and 1.0 part by weight of the organic nucleating agent (B) were uniformly extruded by using a twin screw extruder (?: 40 mm, L / D = 44) to prepare a polyester resin composition pellet.
<실험예 ： 폴리에스터 수지 조성물의 물성 측정 > <Experimental Example: Measurement of Physical Properties of Polyester Resin Composition>
상기 실시예 1， 2, 및 비교예 1 내지 7에서 제조한 펠렛을 각각 사출기를 이용하여 사출온도 285 °C에서 동일하게 사출한 후， 사출된 시험편을 23±2 °C, 50±5% 상대습도 조건 하에서 상태 조절을 하고， 하기와 같은 방법으로 각각의 물성을 측정하였다. 그 결과를 하기 표 1에 나타내었다. The pellets prepared in Examples 1 and 2 and Comparative Examples 1 to 7 were injection-molded at an injection temperature of 285 ° C using an injection machine, respectively, and the injection-molded specimens were subjected to a test at 23 ± 2 ° C and 50 ± 5% The conditions were adjusted under the humidity conditions, and the physical properties were measured by the following method. The results are shown in Table 1 below.
1) 인장강도 및 굴곡강도: ASTM D 638에 의거하여 측정용 시편을 만들고， 만능재료시험기 (Universal Testing Machine, Zwick Roe 11 Z010)를 이용하여 인장강도 및 굴곡강도를 측정하였다.  1) Tensile Strength and Flexural Strength: A test specimen was prepared according to ASTM D 638, and tensile strength and flexural strength were measured using a universal testing machine (Zwick Roe 11 Z010).
2) 층격강도: ASTM D256에 의거하여 측정용 시편을 만들고， 아이조드 충격기 (impact tester, Yasuda)를 사용하여 층격강도를 측정하였다.  2) Strength of Strength: A test specimen was prepared in accordance with ASTM D256, and the tensile strength was measured using an impact tester (Yasuda).
3) 내열도: ASTM D648에 의거하여 측정용 시편을 만들고， 열변형온도를 측정기 (HDT tester, Toyoseiki)를 사용하여 내열도를 측정하였다.  3) Heat resistance: A test specimen was prepared in accordance with ASTM D648, and heat resistance was measured using a heat distortion temperature measuring device (HDT tester, Toyoseiki).
4) 결정화 온도: 시차주사열량계 (Differential Scanning Calorimeter, DSC, 장치명: DSC 8000， 제조사: PerkinElmer)를 이용하여 중합체의 결정화 온도를 측정하였다. 구체적으로는 중합체를 310°C까지 가열한 후 5분 동안 유지하고， 30°C까지 온도를 내린 후 다시 온도를 증가시켰다. 이때 온도의 상승속도와 하강속도는 각각 10°C/min으로 조절하였다. 결정화 온도는 온도를 감소시키면서 나타나는 곡선으로부터 발열 괴크의 최대 지점을 결정화 온도로 하였다. 4) Crystallization temperature: The crystallization temperature of the polymer was measured using a differential scanning calorimeter (DSC, DSC 8000, manufacturer: PerkinElmer). Specifically, the polymer was heated to 310 ° C, held for 5 minutes, cooled to 30 ° C, and then increased in temperature. At this time, the temperature rise rate and the fall rate were adjusted to 10 ° C / min, respectively. The crystallization temperature was defined as the crystallization temperature at the maximum point of the exothermic horn from the curve appearing while decreasing the temperature.
5) 냉각시간 (사출공정): 상기 폴리에스터 수지 조성물을 이용한 시편 제조시 ASTM 인장 시편 금형에 사출된 조성물이 고화되어 금형으로부터 안정적으로 분리되는 최단 시간 (사출 냉각 시간)을 측정하였다. 5) Cooling Time (Injection Process): ASTM tensile test specimen mold solidified during molding of specimen using the above polyester resin composition, And the shortest time (injection cooling time) for stable separation was measured.
【표 11  [Table 11
Figure imgf000023_0001
실험결과， 무기 핵제와 유기 핵제를 흔합 사용한 실시예 1 및 2의 폴리에스터 수지 조성물은， 핵제를 사용하지 않은 비교예 1과 비교하여 동등 수준의 기계적 특성을 나타내면서도 결정화 온도 및 결정화 속도가 크게 증가하였다. 또， 유기 핵제 만을 단독 사용한 비교예 2와 비교하여， 기계적 강도 특성 면에서는 효과가 다소 감소하였으나， 결정화 온도 및 결정화 속도는 크게 증가하였다. 반면， 무기 핵제만을 단독 사용한 비교예 3과 비교했을 때， 결정화 온도 및 속도는 거의 동등 수준의 결과를 나타내었으나, 기계적 특성 면에서는 보다 우수한 효과를 나타내었다. 상기와 같은 결과로부터， 무기 핵제와 유기 핵제꾀 흔합 사용에 의해 결정화 속도를 증가시키고， 동시에 기계적 특성과 이형성을 발란스 좋게 개선시킬 수 있¥을 알 수 있다.
Figure imgf000023_0001
As a result, it was found that the polyester resin compositions of Examples 1 and 2, in which an inorganic nucleating agent and an organic nucleating agent were fused, exhibited substantially the same mechanical properties as those of Comparative Example 1 in which no nucleating agent was used, Respectively. In comparison with Comparative Example 2 in which only the organic nucleating agent was used alone, the effect was somewhat reduced in terms of mechanical strength, but the crystallization temperature and crystallization rate were greatly increased. On the other hand, when compared with Comparative Example 3 using only an inorganic nucleating agent, the crystallization temperature and speed showed almost the same level of results, but the effect was more excellent in terms of mechanical properties. From the above results, it can be seen that the use of the inorganic nucleating agent and the organic nucleating agent can increase the crystallization speed and at the same time improve the mechanical properties and the releasability.
또， PET와 같은 이종의 폴리에스터 수지를 흔합 사용한 비교예 4의 경우 PCT 함량 조건을 층족하지 못함에 따라 이형성이 크게 저하되었으며， 또 함께 사용된 PET로 인해 내열도의 저하가 발생한 것을 확인할 수 있다. 또， 비교예 5와 같이 HDPE가 과량으로 사용된 경우， 결정화 속도의 향상 효과는 미미하고 내열도가 크게 저하되었으며， 또 외관에 심한 플로우마크 (흐름 자국)가 발생하였다. In addition, in Comparative Example 4 in which a different type of polyester resin such as PET was used, the moldability was largely lowered due to the inability to satisfy the PCT content condition, and it was confirmed that the heat resistance was lowered due to the PET used together . In addition, when HDPE was used in an excessive amount as in Comparative Example 5, the effect of improving the crystallization rate was insignificant, the heat resistance was greatly lowered, and a flow mark (flow mark) was generated in appearance.
또, 질화물계 무기 핵제 대신에 종래의 몬탄산 금속염의 무기 핵제를 고밀도 폴리에틸렌계 유기 핵제와 조합 사용한 비교예 6 , 및 고밀도 폴리에틸렌계 유기 핵제 대신에 저밀도 폴리에틸렌계 유기 핵제를 조합 사용한 비교예 7의 경우， 실시예 1 및 2와 비교하여 결정화 온도가 저하되고， 넁각 시간이 크게 증가하였다. 이로부터 질화물계 무기 핵제와 고밀도 플리에틸렌계 유기 핵제의 조합 사용을 통해 보다 우수한 결정화 속도 개선 효과를 얻을 수 있음을 확인할 수 있다.  Comparative Example 6 in which an inorganic nucleating agent of a conventional montmethane metal salt was used in combination with a high density polyethylene type organic nucleating agent and Comparative Example 7 in which a low density polyethylene type organic nucleating agent was used in place of the high density polyethylene type organic nucleating agent was used in place of the nitride type inorganic nucleating agent , The crystallization temperature was lowered and the aging time was significantly increased as compared with Examples 1 and 2. From this, it can be confirmed that a better crystallization speed improving effect can be obtained by using a combination of a nitride-based inorganic nucleating agent and a high-density polyethylene-based organic nucleating agent.
한편， 실시예 1과 2를 비교했을 때 층격보강제를 더 높은 함향으로 포함하는 실시예 1의 폴리에스터 수지 조성물은， 실시예 2와 비교하여 결정화 온도 및 속도 면에서는 동등 수준의 결과를 나타내었으나， 층격 보강제의 증량으로 인해 인장 강도를 비롯한 기계적 특성이 보다 개선된 효과를 나타내었다.  On the other hand, when comparing Examples 1 and 2, the polyester resin composition of Example 1, which included the stratiform enhancer at a higher inclination, showed the same level of crystallization temperature and speed as compared with Example 2, The mechanical properties including tensile strength were improved due to the increase of the modifier.

Claims

【청구범위】 Claims:
【청구항 1】  [Claim 1]
테레프탈산을 포함하는 디카르복실산 유래 반복단위와， 1，4- 사이클로핵산디메탄을을 포함하는 디을 유래 반복단위를 포함하는 폴리에스터 수지 60 내지 80중량 및 충전재 20 내지 40중량 %를 포함하는 흔합물 100중량부에 대해，  Comprising 60 to 80% by weight of a dicarboxylic acid-derived repeating unit containing terephthalic acid, a polyester resin containing a repeating unit derived from diester containing 1,4-cyclohexane dimethane and 20 to 40% by weight of a filler, For 100 parts by weight of the mixture,
질화물계 무기 핵제 0.01 내지 2중량부， 및  0.01 to 2 parts by weight of a nitride-based inorganic nucleating agent, and
0.92 g/cm3 이상의 고밀도 폴리에틸렌계 유기 핵제 0. 1 내지 5중량부를 포함하는, 폴리에스터 수지 조성물. And 0.1 to 5 parts by weight of a high-density polyethylene-based organic nucleating agent of 0.92 g / cm 3 or more.
【청구항 2】 [Claim 2]
제 1항에 있어서，  The method according to claim 1,
상기 무기 핵제와 유기 핵제는 1 : 2 내지 1 : 20의 중량비로 포함되는， 폴리에스터 수지 조성물.  Wherein the inorganic nucleating agent and the organic nucleating agent are contained in a weight ratio of 1: 2 to 1:20.
【청구항 3] [3]
제 1항에 있어서，  The method according to claim 1,
상기 무기 핵제는 질화붕소， 질화알루미늄， 질화규소, 질화티타늄， 질화탄탈륨， 질화바나듬， 질화크름， 질화몰리브덴， 질화니오브 및 질화텅스텐으로 이루어진 군에서 선택되는 어느 하나 또는 둘 이상의 흔합물을 포함하는， 폴리에스터 수지 조성물.  Wherein the inorganic nucleating agent is at least one selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, titanium nitride, tantalum nitride, vanadium nitrides, nitrile nitride, molybdenum nitride, niobium nitride, and tungsten nitride. Polyester resin composition.
【청구항 4】 Claim 4
제 1항에 있어서，  The method according to claim 1,
상기 무기 핵제는 질화붕소를 포함하는， 폴리에스터 수지 조성물.  Wherein the inorganic nucleating agent comprises boron nitride.
【청구항 5] [Claim 5]
거 U항에 있어서，  In the above,
상기 유기 핵제는 0.95 내지 1.0 g/cm3의 밀도를 갖는 고밀도 폴리에틸렌인, 폴리에스터 수지 조성물. The organic nucleating agent has a high density of 0.95 to 1.0 g / cm &lt; 3 &gt; Wherein the polyester resin composition is a polyethylene resin.
【청구항 6] [Claim 6]
거 U항에 있어서，  In the above,
상기 폴리에스터 수지는 폴리사이클로핵실렌디메틸렌 테레프탈레이트 수지인， 폴리에스터 수지 조성물.  Wherein the polyester resin is a polycyclohexenylsilylene dimethylene terephthalate resin.
【청구항 7】 7.
거 U항에 있어서，  In the above,
상기 폴리에스터 수지는 고유 점도가 0.50 내지 1.2dl /g인 폴리에스터 수지 조성물.  Wherein the polyester resin has an intrinsic viscosity of 0.50 to 1.2 dl / g.
【청구항 8] [8]
제 1항에 있어서，  The method according to claim 1,
상기 충전재는 침상의 무기층전재를 포함하는， 폴리에스터 수지 조성물.  Wherein the filler comprises an acicular inorganic layer transfer material.
【청구항 9】 [Claim 9]
게 1항에 있어서，  In Item 1,
상기 층전재는 유리섬유， 워러^트나이트， 티탄산칼슘휘스커， 및 붕산알루미늄휘스커로 이루어진 군에서 선택되는 1종 이상을 포함하는， 폴리에스터 수지 조성물.  Wherein the layer transfer material comprises at least one selected from the group consisting of glass fiber, warultonite, calcium titanate whisker, and aluminum borate whisker.
【청구항 10】 Claim 10
제 1항에 있어서，  The method according to claim 1,
상기 충전재는 평균 길이가 0. 1 내지 20圆이고， 종횡비가 10 내지 Wherein the filler has an average length of 0.1 to 20 mm and an aspect ratio of 10 to &lt; RTI ID = 0.0 &gt;
2000인 유리섬유를 포함하는， 폴리에스터 수지 조성물. Lt; RTI ID = 0.0 &gt; 2000. &Lt; / RTI &gt;
【청구항 11】 제 1항에 있어서， Claim 11 The method according to claim 1,
층격 보강제， 산화안정제， 내가수분해제， 가소제， 착색 안료， 활제， 광안정제， 트랜스에스터화반응 억제제， 커플링제， 사슬 연장제， 자외선 안정제， 착색 방지제, 무광택제， 탈취제， 난연제， 내후성첨가제， 대전방지제， 이형제， 이온 교환제， 및 광흡수제로 이루어진 군에서 선택되는 1종 이상의 첨가제를 더 포함하는， 폴리에스터 수지 조성물.  A colorant, a lubricant, a light stabilizer, a transesterification inhibitor, a coupling agent, a chain extender, a UV stabilizer, a coloring agent, a matting agent, a deodorant, a flame retardant, a weathering additive, Wherein the polyester resin composition further comprises at least one additive selected from the group consisting of an antistatic agent, a releasing agent, an ion exchanger, and a light absorber.
【청구항 12] [12]
제 11항에 있어서，  12. The method of claim 11,
상기 층격보강제는 불포화니트릴 -방향족비닐 공중합체， 불포화니트릴-방향족비닐 -글리시딜 (메타)아크릴레이트 공중합체， 불포화니트릴-방향족비닐-말레산무수물 공중합체， 에틸렌-아크릴레이트- 글리시딜 메타크릴레이트 공중합체， 글리시딜 (메타)아크릴레이트가 그라프트된 비닐계 공중합체， 할로겐이 치환된 비닐계 공중합체， 방향족비닐-방향족 말레이미드-말레산 무수물 공중합체 방향족비닐- 불포화니트릴-방향족 말레이미드 공증합체, 방향족비닐 - α -메틸 방향족비닐 공중합체 및 방향족비닐-불포화니트릴 - α -메틸 방향족비닐 공중합체로 이루어진 군에서 선택되는 어느 하나 또는 둘 이상의 화합물을 포함하는, 폴리에스터 수지 조성물.  The weight modifier may be selected from the group consisting of unsaturated nitrile-aromatic vinyl copolymers, unsaturated nitrile-aromatic vinyl-glycidyl (meth) acrylate copolymers, unsaturated nitrile-aromatic vinyl-maleic anhydride copolymers, ethylene- Acrylate-grafted vinyl copolymers, halogen-substituted vinyl copolymers, aromatic vinyl-aromatic maleimide-maleic anhydride copolymers, aromatic vinyl-unsaturated nitrile-aromatic (meth) An aromatic vinyl-α-methyl aromatic vinyl copolymer, and an aromatic vinyl-unsaturated nitrile-α-methyl aromatic vinyl copolymer.
【청구항 13】 Claim 13
제 1항에 있어서，  The method according to claim 1,
충격보강제 및 산화방지제를 더 포함하며，  An impact modifier, and an antioxidant,
상기 산화방지제는 페놀계 제 1산화방지제와 인계 제 2산화방지제를 2 : 1 내지 1 : 2의 중량비로 포함하는， 폴리에스터 수지 조성물.  Wherein the antioxidant comprises a phenol-based antioxidant and a phosphorus-based antioxidant in a weight ratio of 2: 1 to 1: 2.
【청구항 14] [14]
제 1항에 있어서，  The method according to claim 1,
상기 폴리에스터 수지로서 폴리사이클로핵실렌디메틸렌 테레프탈레이트 수지 60 내지 80중량 ¾；, 및 상기 층전재로서 유리섬유 20 내지 40중량 %를 포함하는 흔합물 100중량부에 대하여 , As the above-mentioned polyester resin, polycyclohexanediyldimethylene 60 to 80 parts by weight of a terephthalate resin and 20 to 40 parts by weight of glass fiber as a layer transfer material,
상기 무기 핵제로서 질화붕소 0.01 내지 2중량부， 및 유기 핵제로서 0.92 내지 1.0 g/cu의 고밀도 폴리에틸렌 0.1 내지 5중량부를 포함하되， 상기 무기 핵제와 유기 핵제의 중량비가 1:5 내지 1:10이고，  0.01 to 2 parts by weight of boron nitride as the inorganic nucleating agent and 0.1 to 5 parts by weight of high density polyethylene having an organic nucleating agent of 0.92 to 1.0 g / cu, wherein the weight ratio of the inorganic nucleating agent to the organic nucleating agent is 1: 5 to 1:10 ,
충격 보강제 및 산화방지제를 더 포함하며，  An impact modifier, and an antioxidant,
상기 산화방지제는 페놀계 게 1산화방지제와 인계 제 2산화방지제를 2:1 내지 1:2의 중량비로 포함하는， 폴리에스터 수지 조성물. 【청구항 15】  Wherein the antioxidant comprises a phenol-based antioxidant and a phosphorus-based antioxidant in a weight ratio of 2: 1 to 1: 2. 15.
제 1항에 있어서，  The method according to claim 1,
결정화 온도가 245 °C 이상인， 폴리에스터 수지 조성물. 【청구항 16] And a crystallization temperature of at least 245 ° C. 16. The method of claim 16,
게 1항 내지 제 15항 중 어느 한 항에 따른 폴리에스터 수지 조성물을 포함하는 성형품.  15. A molded article comprising the polyester resin composition according to any one of claims 1 to 15.
PCT/KR2018/009819 2017-09-22 2018-08-24 Polyester resin composition WO2019059544A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2017-0122818 2017-09-22
KR1020170122818A KR102362662B1 (en) 2017-09-22 2017-09-22 Polyester resin composition

Publications (1)

Publication Number Publication Date
WO2019059544A1 true WO2019059544A1 (en) 2019-03-28

Family

ID=65809808

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/009819 WO2019059544A1 (en) 2017-09-22 2018-08-24 Polyester resin composition

Country Status (2)

Country Link
KR (1) KR102362662B1 (en)
WO (1) WO2019059544A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102419077B1 (en) * 2022-01-03 2022-07-07 신영철 Automotive electronics plastic composition and automotive electronics plastic manufactured therefrom

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040116572A1 (en) * 2002-12-17 2004-06-17 Herve Cartier Polyethylene terephthalate compositions
US20070088113A1 (en) * 2005-10-07 2007-04-19 Fujifilm Corporation Resin composite material and electronic device component
US20150105521A1 (en) * 2012-06-29 2015-04-16 Teijin Limited Resin composition
KR20160110160A (en) * 2015-03-09 2016-09-21 란세스 도이치란트 게엠베하 Thermoplastic moulding compounds
WO2017023173A1 (en) * 2015-08-04 2017-02-09 Furanix Technologies B.V. Masterbatch polyester composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040116572A1 (en) * 2002-12-17 2004-06-17 Herve Cartier Polyethylene terephthalate compositions
US20070088113A1 (en) * 2005-10-07 2007-04-19 Fujifilm Corporation Resin composite material and electronic device component
US20150105521A1 (en) * 2012-06-29 2015-04-16 Teijin Limited Resin composition
KR20160110160A (en) * 2015-03-09 2016-09-21 란세스 도이치란트 게엠베하 Thermoplastic moulding compounds
WO2017023173A1 (en) * 2015-08-04 2017-02-09 Furanix Technologies B.V. Masterbatch polyester composition

Also Published As

Publication number Publication date
KR20190033993A (en) 2019-04-01
KR102362662B1 (en) 2022-02-11

Similar Documents

Publication Publication Date Title
ES2698355T3 (en) Composition of polymer resin that has excellent impact resistance or heat resistance
US4859732A (en) Reinforced molding composition based on poly(1,4-cyclohexylene dimethylene terephthalate) having improved crystallization characteristics
WO2016179770A1 (en) Pbt engineering plastic composition used for nmt
JP5396690B2 (en) An inorganic reinforced polyester resin composition and a method for improving the surface appearance of a molded article using the same.
CN102093677A (en) Glass fiber-reinforced polyester resin composition and molded product using the same
KR101690829B1 (en) Thermoplastic resin composition having excellent Impact resistance and light stability
KR101850211B1 (en) Polycarbonate resin composition having excellent chemical resistance and metallic color
KR102169415B1 (en) Polycyclohexylenedimethylene terephthalate resin composition
WO2019059544A1 (en) Polyester resin composition
JP2020532630A (en) Thermoplastic polyester molding composition
KR101486567B1 (en) Thermoplastic resin composition and molded product using the same
KR100846861B1 (en) Composition Of Polyester resin
JPS59531B2 (en) polyester resin composition
WO2019054665A1 (en) Polyester resin composition
KR20170003868A (en) Thermoplastic resin composition and article comprising the same
CN110776725B (en) Polyester resin composition and article formed using the same
WO2017119647A1 (en) Polymeric resin composition for metal bonding, metal-resin composite and article using same
KR101102596B1 (en) Wholly aromatic liquid crystalline polyester resin compound with enhanced releasing property and method for preparing the same
KR101946077B1 (en) A thermoplastic composition, method of producing the same, and articles made therefrom
JP3761598B2 (en) Polybutylene terephthalate resin molded product
KR101786185B1 (en) Polyester resin composition and article comprising the same
KR101829959B1 (en) Thermoplastic resin composition and article comprising the same
JP2020152770A (en) Polyester-based resin composition
JP2004331967A (en) Injection-molded article produced from biodegradable aromatic polyester blend composition and method for producing the same
JP2006219611A (en) Polybutylene terephthalate resin composition and molded article made thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18858052

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18858052

Country of ref document: EP

Kind code of ref document: A1