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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

• the present invention relates to a polyester / polycarbonate blend, and more particularly, to a polyester / polycarbonate blend having excellent thermal stability and color stability, high transparency, and excellent flame retardancy and compatibility between compositions.
• polyester Since polyester has excellent mechanical strength, heat resistance, transparency and gas barrier properties, polyester is most suitable as a material for beverage filling containers such as juices, soft drinks, carbonated drinks, packaging films, audio and video films, etc. It is used in large quantities. Sheets and plates of polyester have good transparency and excellent mechanical strength, and are widely used as materials for cases, boxes, partitions, store shelves, protective panels, blister packaging, building materials, interior and exterior materials, and the like. As the use of new polyester, which has recently attracted attention, an example of forming a thick plastic sheet and using it as a building interior material, a molding signboard, and the like is increasing.
• polyester has low heat resistance compared to other competitive resins used for sheet use, such as acrylic (PMMA) or polycarbonate (PC), and may not be suitable for outdoor exterior materials having severe seasonal temperature changes. Accordingly, various technical attempts have been made to improve the heat resistance of the polyester, and among them, there is a blending technique with polycarbonate (PC).
• PC polycarbonate
• PET polyethylene terephthalate
• polycarbonate which are typical examples of polyester
• HDT heat distortion temperature
• the polyester copolymerized with 1,4-cyclohexanedimethanol is a copolyester having a basic structure of terephthalic acid, ethylene glycol, and 1,4-cyclohexanedimethanol (CHDM), and PCTG (glycol-modified poly ( Also referred to as 1,4-cyclohexylenedimethylene terephthalate (PET) or CHDM-modified polyethylene terephthalate (PETG) (see US Pat. No. 7,964,258)
• the PCTG contains no harmful substances to the human body and is environmentally friendly, with excellent formability, processability and transparency.
• the PCTG can be prepared by using various catalysts, but commercially produced by using titanium catalysts. The titanium catalysts have better polymerization reactivity than other catalysts, but the color stability of blends depends on their content. Has the disadvantage of inhibiting yellowing of the blend.
• polyester / polycarbonate (PC) blends in which 1,4-cyclohexanedimethanol is copolymerized
• studies for improving compatibility between two resins have been actively conducted since the 80's.
• Polyester / PC blends copolymerized with 1,4-cyclohexanedimethanol may express new complementary physical properties depending on the composition of each component, but the heat resistance does not increase proportionally with increasing polyester content.
• heat resistance increases in proportion to the content only in a region where the content of polyester is low.
• the color of the polyester and PC blend is changed by the titanium catalyst, thereby limiting its use.
• polyester / polycarbonate blends with excellent thermal stability, color stability, flame retardancy and compatibility between compositions.
• the present invention (a) comprises a dicarboxylic acid component containing 50 to 100 mol% terephthalic acid residue, and 40 to 90 mol% 1,4-cyclohexanedimethanol residue 10 to 50 weight percent of a first polyester comprising a diol component; (b) a dicarboxylic acid component comprising from 50 to 100 mole percent terephthalic acid residues, and a diol component comprising from 1 to 80 mole percent cyclohexanedimethanol residues and from 1 to 60 mole percent isosorbide residues 3 to 30% by weight of the second polyester; And (c) 20 to 87 weight percent polycarbonate.
• the polyester / polycarbonate blend according to the present invention is an agent in which 1,4-cyclohexanedimethanol is copolymerized with 40 to 90 mol% of the first polyester, cyclohexanedimethanol and isosorbide copolymerized with respect to the total diol component.
• 2 polyester and polycarbonate (PC) wherein the second polyester increases the compatibility of the first polyester and polycarbonate, and improves the flame retardancy of the entire blend.
• the polyester / polycarbonate blend of the present invention is excellent in color stability (transparency) with a color-b (yellowness) of 0 or less when germanium is included (germanium is used as a catalyst when preparing polyester), The thermal stability (heat resistance) is excellent.
• the term “polyester” includes “copolyester”, meaning a synthetic polymer prepared by the polycondensation reaction of one or more difunctional carboxylic acids with one or more difunctional hydroxyl compounds. do.
• the difunctional carboxylic acid is a dicarboxylic acid and the difunctional hydroxyl compound is a dihydric alcohol such as glycol or diol.
• the term “residue” means a certain part or unit which is included in the result of the chemical reaction when the specific compound participates in the chemical reaction and is derived from the specific compound.
• each of "dicarboxylic acid residue” and “diol (glycol) residue” is derived from a diol component or part derived from a dicarboxylic acid component in a polyester formed by an esterification reaction or a polycondensation reaction.
• the dicarboxylic acid residue may be a dicarboxylic acid monomer or an acid halide or ester thereof (e.g., lower alkyl ester having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester). , Salts, anhydrides, or mixtures thereof.
• the terms “dicarboxylic acid”, “terephthalic acid” and the like are useful for the polycondensation process with a diol for producing a high molecular weight polyester, dicarboxylic acid (terephthalic acid, etc.) and its dika And any derivatives of leric acid, such as acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof.
• the polyester / polycarbonate blend according to the present invention is for improving the thermal stability, color stability, flame retardancy, compatibility, etc. of the polyester / polycarbonate blend, and is 1,4-cyclohexanedimethanol (1,4-cyclohexanedimethanol).
• a dicarboxylic acid component containing 50 to 100 mol% of terephthalic acid residue and a diol component containing 40 to 90 mol% of 1,4-cyclohexanedimethanol residue are copolymerized.
• Copolyester a dicarboxylic acid component containing 50 to 100 mol% of terephthalic acid residue and a diol component containing 40 to 90 mol% of 1,4-cyclohexanedimethanol residue are copolymerized.
• the dicarboxylic acid component of the first polyester contains 50 to 100 mol%, for example, 60 to 99.9 mol%, specifically 70 to 99.5 mol%, of the terephthalic acid moiety relative to the total dicarboxylic acid component.
• aromatic dicarboxylic acid residues having 8 to 20 carbon atoms, preferably 8 to 14 carbon atoms (excluding terephthalic acid residues), aliphatic dicar having 4 to 20 carbon atoms and preferably 4 to 12 carbon atoms.
• 0 to 50 mol% for example, 0.1 to 40 mol%, specifically 0.5 to 30 mol%, of dicarboxylic acid residues such as an acid residue and a mixture thereof.
• naphthalenedicarboxylic acid such as isophthalic acid and 2, 6- naphthalenedicarboxylic acid, and diphenyl dicarboxylic acid except terephthalic acid.
• Aromatic dicarboxylic acids typically used in the production of polyester resins such as 4,4'-steelbendicarboxylic acid, 2,5-furandicarboxylic acid, and 2,5-thiophenedicarboxylic acid
• Illustrative examples of the aliphatic dicarboxylic acids capable of forming the aliphatic dicarboxylic acid residues include cyclohexane dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid.
• Linear, branched, or cyclic aliphatic dichas commonly used in the preparation of polyester resins such as carboxylic acid, phthalic acid, sebacic acid, succinic acid, isodecyl succinic acid, maleic acid, fumaric acid, adipic acid, glutaric acid, azeraiic acid, and the like.
• carboxylic acid components Can.
• the dicarboxylic acid residues other than the terephthalic acid residues when the dicarboxylic acid residues other than the terephthalic acid residues are included, when the content of the dicarboxylic acid residues is too small or too large, the effect of improving physical properties is insufficient, or rather, the physical properties of the polyester resin are lowered. There is a concern.
• the diol component of the first polyester is 40 to 90 mol%, preferably 45 to 80 mol%, more preferably 50 to 70 mol% of 1,4-cyclohexanedimethanol based on the total diol component ( 1,4-cyclohexanedimethanol (CHDM) residue, and 10 to 60 mol%, preferably 20 to 55 mol%, more preferably 30 to 50 mol% ethylene glycol residues, if necessary, polyester resin
• aliphatic diol residues having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms (excluding 1,4-cyclohexanedimethanol residues and ethylene glycol residues)
• 8 to 40 carbon atoms and preferably 8 to 8 carbon atoms 0 to 50 mol%, for example, 0.1 to 40 mol%, specifically 0.5 to 30 mol%, of diol residues such as 33 aromatic diol residues and mixtures thereof.
• Diols capable of forming the aliphatic diol residues include diethylene glycol, triethylene glycol, propanediol (1,2-propanediol, 1,3-propanediol, etc.), 1,4-butanediol, pentanediol, hexanediol (1,6-hexanediol, etc.), neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexane Linear, branched, or cyclic aliphatic diols such as dimethanol, 1,3-cyclohexanedimethanol, tetramethylcyclobutanediol, and the like, and diols capable of forming the aromatic diol moiety include polyoxyethylene- ( 2.0) -2,2-bis (4-hydroxy
• the impact strength rapidly increases as the content of the 1,4-cyclohexanedimethanol residues increases It was confirmed.
• the diol residue except the said 1, 4- cyclohexane dimethanol residue and the ethylene glycol residue is a moldability of the copolymer which uses only 1, 4- cyclohexane dimethanol and ethylene glycol as a raw material, etc. It is used to improve physical properties.
• the impact strength may be insufficient or the transparency may be lowered. have.
• the content of the ethylene glycol residues is less than 10 mol% based on the total diol components, there is a fear that the polymerization reaction is difficult, and when it exceeds 90 mol% there is a fear that the impact strength is lowered.
• the content of the first polyester is 10 to 50% by weight, preferably 20 to 45% by weight, more preferably 30 to 40% by weight, based on the total polyester / polycarbonate blend. If the first polyester content is less than 10% by weight based on the total blend, the transparency may be lowered. If the content of the first polyester exceeds 50% by weight, the heat resistance may be lowered.
• the weight average molecular weight (Mw) of the first polyester is, for example, 30,000 to 70,000, if the weight average molecular weight is out of the above range, there is a fear that the physical properties of the blend is lowered.
• the second polyester used in the present invention is a diol including dicarboxylic acid components such as terephthalic acid residues and cyclohexanedimethanol residues and isosorbide (1,4: 3,6-dianhydroglucitol) residues.
• the component is a copolymerized copolyester. This copolyester is currently produced by SK Chemicals under the brand ECOZEN.
• the dicarboxylic acid component of the second polyester the same dicarboxylic acid component as defined in the dicarboxylic acid component of the first polyester can be used.
• the diol component of the second polyester is 1 to 80 mole%, preferably 5 to 70 mole%, more preferably 10 to 60 mole% of cyclohexanedimethanol (1,2- relative to the total diol component).
• Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, etc.) residues 1 to 60 mol%, preferably 10 to 55 mol%, more preferably 20 to 50 mol% Isosorbide moiety of and an aliphatic diol moiety having 1 to 80 mole%, preferably 5 to 60 mole%, more preferably 10 to 50 mole% carbon atoms of 2 to 20, preferably 2 to 12 carbon atoms (cyclo Diol residues such as hexanedimethanol residues and isosorbide residues), aromatic diol residues having 8 to 40 carbon atoms, preferably 8 to 33 carbon atoms, and mixtures thereof.
• Diols capable of forming the aliphatic diol residues include ethylene glycol, diethylene glycol, triethylene glycol, propanediol (1,2-propanediol, 1,3-propanediol, etc.), 1,4-butanediol, and pentanediol.
• the impact strength may be insufficient or the transparency may be lowered, and if it exceeds 80 mol%, There exists a possibility that processing of polyester resin will become difficult.
• the content of the isosorbide moiety is less than 1 mol% with respect to the total diol component, there is a fear that the heat resistance or chemical resistance of the polyester resin (second polyester) to be produced may be insufficient, and when it exceeds 60 mol%, Appearance of the polyester resin may be degraded or yellowing may occur.
• the content of the diol residues (excluding cyclohexanedimethanol residues and isosorbide residues) is less than 1 mol% based on the total diol components, there is a possibility that the effect of improving physical properties may be insufficient. When it exceeds mol%, there exists a possibility that the physical property of polyester may fall rather.
• the second polyester has environmentally friendly, excellent thermal and mechanical properties.
• the second polyester is a part of the residue of the diol component is derived from isosorbide, it can greatly improve the mechanical properties, heat resistance, flame retardancy, etc. of the polyester, and mixed with polycarbonate (PC) and the first polyester This can maximize complementary effects (such as increased compatibility).
• the second polyester is used as a compatibilizer for the first polyester / PC blend and, in particular, improves flame retardancy.
• the impact strength of the second polyester increases greatly as the content of cyclohexanedimethanol increases.
• the content of the second polyester is 3 to 30% by weight, preferably 4 to 25% by weight, more preferably 5 to 20% by weight, based on the total polyester / polycarbonate blend.
• the content of the second polyester is less than 3% by weight based on the total blend, there is a fear that the heat resistance, flame retardancy and compatibility of the blend may be lowered. If the content of the second polyester exceeds 30% by weight, the transparency may be lowered. .
• the weight average molecular weight (Mw) of the second polyester is, for example, 30,000 to 70,000, if the weight average molecular weight is out of the above range, there is a fear that the physical properties of the blend is lowered.
• the first and second polyester may be prepared by a conventional polyester production method, for example, esterifying the dicarboxylic acid and the diol compound, and polycondensing the esterification reaction product. (Poly-condensation) can be prepared through the reaction. Specifically, the step of esterifying the dicarboxylic acid and diol compound, esterification of the dicarboxylic acid and diol compound at a pressure of 0 to 10.0 kg / cm2 and 150 to 300 °C temperature for 1 to 24 hours Reaction or transesterification.
• the esterification conditions may be appropriately adjusted according to the specific properties of the polyester to be prepared, the molar ratio of the dicarboxylic acid component and glycol, process conditions, and the like.
• esterification conditions are 0 to 5.0 kg / cm 2, more preferably 0.1 to 3.0 kg / cm 2, 200 to 270 ° C., more preferably 240 to 260 ° C., 1
• a reaction time of from 15 hours to more preferably 2 to 8 hours can be exemplified.
• the molar ratio of the dicarboxylic acid component and the diol component participating in the esterification reaction may be 1: 1.05 to 1: 3.0. If the molar ratio of the diol component to the dicarboxylic acid component is less than 1.05, the unreacted dicarboxylic acid component may remain during the polymerization reaction and the transparency of the resin may be lowered.
• the polymerization reaction rate May be lowered or the productivity of the resin may be lowered.
• Catalysts may be selectively used to improve process time and yield of the esterification reaction, and the esterification reaction may be performed in a batch or continuous manner, and each raw material may be added separately, but diol It is preferable to add in the form of the slurry which mixed the dicarboxylic acid component with the component.
• a diol component such as isosorbide which is solid at room temperature can be dissolved in water or ethylene glycol, and then mixed with a dicarboxylic acid component such as terephthalic acid to form a slurry.
• water may be added to a slurry containing a mixture of dicarboxylic acid components, isosorbide, and ethylene glycol, to increase the solubility of the isosorbide. It is also possible to use a slurry in which the beads are molten.
• the poly-condensation reaction of the esterification product, the esterification reaction product of the dicarboxylic acid component and the diol component 1 at a temperature of 150 to 300 °C and a reduced pressure of 400 to 0.01 mmHg To react for 24 hours.
• This polycondensation reaction may be carried out at a reaction temperature of preferably 200 to 290 ° C, more preferably 260 to 280 ° C, and reduced pressure of preferably 100 to 0.05 mmHg, more preferably 10 to 0.1 mmHg. .
• glycol which is a byproduct of the polycondensation reaction, may be removed.
• the polycondensation reaction when the polycondensation reaction is out of the 400 to 0.01 mmHg reduced pressure range, there is a concern that the byproducts may be insufficient. In addition, when the polycondensation reaction occurs outside the temperature range of 150 to 300 °C, there is a fear that the physical properties of the polyester resin produced.
• the polycondensation reaction can proceed for the required time until the intrinsic viscosity of the final reaction product reaches an appropriate level, for example for an average residence time of 1 to 24 hours.
• the final attained vacuum degree of the polycondensation reaction is less than 2.0 mmHg, and the esterification reaction and the polycondensation reaction may be performed under an inert gas atmosphere.
• additives such as polycondensation catalysts or stabilizers may be used.
• Additives such as polycondensation catalysts or stabilizers may be added to the product of the esterification reaction or transesterification reaction before initiation of the polycondensation reaction, and mixed slurry comprising dicarboxylic acid and diol compound before the esterification reaction. Phase may be added, or may be added during the esterification step.
• a titanium compound, a germanium compound, an antimony compound, an aluminum compound, a tin compound, or a mixture thereof can be used.
• the titanium compound include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate Nitrate, triethanolamine titanate, acetylacetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide / silicon dioxide copolymer, titanium dioxide / zirconium dioxide copolymer, and the like.
• germanium-based compound examples include germanium dioxide (germanium dioxide, GeO 2 ), germanium tetrachloride (germanium tetrachloride, GeCl 4 ), germanium ethyleneglycoxide, germanium acetate, and the like. Coalescing, of these There may be mentioned compounds and the like.
• germanium dioxide may be used, both crystalline and amorphous may be used, and glycol soluble may be used.
• the stabilizer phosphorus compounds such as phosphoric acid, trimethyl phosphate, and triethyl phosphate may be used, and the amount of the stabilizer may be 10 to 200 ppm based on the amount of phosphorus element based on the weight of the final polymer (polyester resin). If the amount of the stabilizer added is less than 10 ppm, the stabilizing effect may be insufficient and the appearance of the final product may change to yellow. In addition, when the addition amount of the stabilizer exceeds 200 ppm it may not be possible to obtain a polymer of the desired high degree of polymerization.
• any conventional polycarbonate used in conventional polyester / polycarbonate blending may be used without limitation, and for example, bisphenol A may be used as a basic material. It is possible to use a variety of general-purpose extrusion and injection polycarbonate prepared by polymerization.
• the polycarbonate may be prepared by a phosgene method (or a solvent method) or a transesterification method (or a melting method).
• the phosgene method is a manufacturing method for reacting bisphenol A with phosgene (polycondensation reaction).
• the interfacial polycondensation reaction proceeds to poly
• the carbonate is obtained in a state dissolved in a solvent. This may be neutralized and washed to remove byproduct inorganic salts, and may be obtained by precipitating polycarbonate into flakes using a petroleum or alcoholic nonsolvent.
• the phosgene method has an advantage that a polymer having an arbitrary molecular weight can be obtained from a low amount to a high molecular weight, and because the reaction conditions are smooth, no special apparatus is required.
• the phosgene method requires an expensive solvent, requires a solvent recovery step and a washing step for completely removing inorganic salts mixed in the resin, and pelletizes through a melting process because the product is obtained in powder or flake form. There is a disadvantage to be done.
• the said transesterification method is a method of obtaining a polycarbonate through polycondensation by ester reaction by mixing bisphenol A and diphenyl carbonate in a suitable compounding ratio, and heat-melting it under high temperature and pressure reduction without a solvent.
• the initial pressure of the reaction is maintained at a pressure of 20 to 30 mmHg and a temperature of 200 to 230 °C, and at the end of the reaction, if the conditions are changed to a pressure of 1 mmHg and temperature of 290 to 300 °C, the melt viscosity of the system rises to a high molecular weight product Can be obtained.
• the transesterification method does not use a solvent and does not require a solvent recovery step, and the resulting resin is obtained in a molten phase, it can be pelletized by extruding from a reaction vessel with an inert gas, thereby simplifying the treatment of the product.
• the facilities such as a gas tight reactor capable of maintaining harsh high temperature and high vacuum reaction conditions are high, and polycarbonates having a high molecular weight cannot be manufactured as compared with the phosgene method.
• the content of the polycarbonate is 20 to 87% by weight, preferably 30 to 76% by weight, more preferably 40 to 65% by weight, based on the total polyester / polycarbonate blend.
• the content of the polycarbonate is less than 20% by weight based on the total blend, the heat resistance of the blend may be lowered.
• the content of the polycarbonate exceeds 87% by weight, the transparency of the blend may be deteriorated or yellowed. have.
• the polycarbonate may be a melt index (Melt Index: MI) of 5 to 40g / 10 minutes (300 °C). If the melt index of the polycarbonate is less than 5 g / 10 minutes (300 ° C.), the workability of the blend may be lowered.
• MI Melt Index
• the weight average molecular weight (Mw) of the polycarbonate is, for example, 20,000 to 60,000. When the weight average molecular weight is out of the above range, there is a possibility that the physical properties of the blend may be lowered.
• the polyester / polycarbonate blend according to the present invention may further comprise germanium in order to improve discoloration (yellowing) of the blend which occurs when the first and second polyesters and polycarbonates are blended.
• the germanium is 10 to 1000 ppm (weight ratio), preferably 20 to 700 ppm (weight ratio), more preferably 50 to 500 ppm (weight ratio), most preferably, relative to the total polyester / polycarbonate blend. Preferably from 100 to 300 ppm (weight ratios).
• the germanium is included, if the germanium content is less than 10 ppm with respect to the total blend, the color of the blend may be discolored. If the content exceeds 1000 ppm, there is no particular advantage, but the price of germanium is high and the manufacturing cost is high.
• the germanium may be included in the form of a germanium catalyst (polycondensation catalyst, germanium-based compound) to include the germanium content range for the entire blend during the first or second polyester polymerization.
• a germanium catalyst polycondensation catalyst, germanium-based compound
• the dicarboxylic acid component and the diol component are 0.2 to 3.0 kg / in the presence of the germanium catalyst (germanium compound). Esterification or transesterification reaction at a pressurization pressure of cm 2 and a temperature of 200 to 300 ° C.
• esterification or transesterification reaction product under reduced pressure 400 to 0.1 mmHg and Germanium
• the esterification or transesterification reaction product under reduced pressure 400 to 0.1 mmHg and Germanium
• preparing a first or second polyester by using a polycondensation reaction at an average residence time of 1 to 10 hours at a temperature of 240 to 300 ° C. and preparing a blend using the same.
• the polyester / polycarbonate blend according to the present invention can be prepared by conventional blending methods, and can be molded, for example, by molding methods such as injection, extrusion and compounding processes.
• conventional additives such as antistatic agents, stabilizers, etc. may be appropriately added, and the amount of the additives may be adjusted to a degree apparent to those skilled in the art, and the present invention is limited by the use of such additives. It doesn't happen.
• the polyester / polycarbonate blend of the present invention has a Color-b (yellowness) of 0 or less, preferably -3 to 0, based on a 3 mm thick specimen after molding.
• the transparency of the specimen is 89% or more, preferably 89 to 92%
• the glass transition temperature (Tg) is 100 °C or more, preferably 100 to 120 °C.
• Both the first polyester and the second polyester have a glass transition temperature of less than 100 ° C., and the blend (two component blend) of the two resins also exhibits a glass transition temperature of less than 100 ° C.
• the polyester / polycarbonate blend (3-component blend) of the present invention has excellent heat resistance compared to the first polyester and second polyester blends (two-component blends) with a heat resistance of 100 ° C. or higher.
• the polyester / polycarbonate blend of the present invention has excellent color stability compared to the second polyester and polycarbonate blend (two-component blend). That is, if the first polyester is not blended, the Color-b value may be 0 or less, or may not have a transparency of 89% or more.
• the compatibility between the polyester and the polycarbonate is not good, and the physical properties of the blend may be unstable, but the polyester / polycarbonate blend of the present invention is the second polyester.
• the compatibility and flame retardancy of the entire blend are increased and the above stable physical properties are exhibited.
• polyester / polycarbonate blends (germanium containing blends) of the present invention using polyesters and polycarbonates prepared under germanium catalysts, for example, polyesters (PCTG, PETG, etc.) prepared under conventional titanium catalysts, etc.
• Color stability (Color-b (yellowness), Color-L (lightness)) and transparency are superior to the used polyester / polycarbonate blend (titanium-containing blend). That is, the titanium containing blend may be discolored by the titanium component to reduce the overall blend color, and the polycarbonate may also be discolored due to the strong reactivity of the titanium component, thereby reducing the color of the entire blend.
• germanium-containing blends have a color-b value of about 1 to 2 superior to titanium-containing blends, and can increase transparency by about 1%. Transparency is usually considered to be a property of resins, but a considerable amount of effort is required to increase it by 1%, but the polyester / polycarbonate blend of the present invention contains germanium, which is comparable to that of an acrylic resin having the best transparency among plastics. It can represent.
• esterification or transesterification reaction product was polycondensed at 400 to 0.1 mmHg under reduced pressure and at a temperature of 240 to 300 ° C for an average residence time of 1 to 10 hours to prepare 4,000 g of the first polyester.
• Table 1 the content units of polycarbonate (PC), first polyester, second polyester (ECOZEN) and polyethylene terephthalate (PET) is in weight percent, 1,4-cyclo Mole% of hexanedimethanol (CHDM) is based on the total diol of the first polyester, the content of germanium (Ge) and titanium (Ti) is weight ratio to the total blend), using a dehumidifying dryer at 120 ° C.
• a 6 hour dry second polyester (product name: ECOZEN, manufacturer: SK Chemicals) and polyethylene terephthalate (PET) were placed in a well-dehumidified container, and mixed (melt compounding) by tumbling at 250 to 280 ° C for about 3 minutes.
• the melt mixture was extruded in an extruder to obtain a polyester / polycarbonate blend in the form of a chip.
• the residence time of the extruder is preferably maintained for about 2 to 30 minutes, the screw speed is low, specifically 100 ⁇ 200rpm extruded so that the polyester resin and polycarbonate resin is sufficiently mixed.
• the polyester / polycarbonate blend copolymerized with cyclohexanedimethanol according to the present invention includes Color-b in the range of -3 to 0, and has a transparency of 89.8% or more and excellent color stability. It is found that Tg is 109 ° C or higher, and HDT is 101 ° C or higher, which is excellent in thermal stability.
• a Ti catalyst is included instead of a Ge catalyst, or PET is used instead (Comparative Examples 1, 2, and 4), Color-b due to deterioration in compatibility, It can be seen that the transparency, etc.

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