KR20190062046A - Polyester-carbonate copolymer and method for preparing same and molded articl by using same - Google Patents

Abstract

Disclosed is a polyester carbonate copolymer which is excellent in processability and transparency while having excellent heat resistance of polyacrylate. The polyester carbonate copolymer includes: a repeating unit represented by chemical formula 1; and a repeating unit represented by chemical formula 2. In chemical formulas 1 and 2, A is a substituted or unsubstituted C_1-C_40 alkylene group or C_6-C_40 arylene group, or a substituted or unsubstituted C_1-C_40 heteroalkylene group or C_2-C_40 heteroarylene group, and may include nitrogen, oxygen, phosphorous, sulfur, silicon, a halogen element or a metal element in a structure thereof, and B is a substituted or unsubstituted C_1-C_20 alkylene group or C_6-C_20 arylene group, or a substituted or unsubstituted C_1-C_20 heteroalkyl group or C_2-C_20 heteroarylene group, and may include nitrogen, oxygen, phosphorous, sulfur, silicon, a halogen element or a metal element in a structure thereof.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyester carbonate copolymer, a method for producing the same, and a molded article using the same. BACKGROUND ART [0002]

More particularly, the present invention relates to a polyester carbonate copolymer having high transparency and high heat resistance, and a process for producing the same.

Polyarylate (PAR) resins are generally produced by interfacial polymerization of bisphenol A and terephthaloyl chloride (TPC), and are excellent in heat resistance and transparency. However, due to high heat resistance, the processability is much lower than that of other engineering plastic resins.

In order to improve the processing performance of these polyarylate resins, they are blended with transparent engineering plastic resins having excellent processability such as polycarbonate (PC) in a compound form. However, since the refractive indexes of the polycarbonate and the polyarylate are similar but not the same, optical performance such as transmittance and haze when used as mixed are lower than those of the original resins, and polycarbonate and polyarylate are synthesized Followed by blending at a constant ratio.

Japanese Patent Application Laid-Open No. 2009-167291 discloses a polyarylate composed of a bisphenol and an aromatic dicarboxylic acid having a bisphenol and an isopropylidene skeleton having a cyclohexane ring structure, but there is a hazard due to the use of a chlorine compound , The interfacial polymerization process is applied, the apparatus cost and the operation cost are high, and the produced copolymer resin has poor processability, so that molding processing such as extrusion and injection is difficult, and it is dissolved in a solvent and used only in the form of film.

Korean Patent Laid-Open Publication No. 2015-0081989 discloses a resin composition in which polycarbonate and polyarylate are mixed, but it is necessary to apply a compound manufacturing method using an extruder by polymerizing each resin individually, and to use a polyarylate and a polycarbonate There is a problem that the compatibility is poor and the polyarylate undergoes color change due to the high temperature when extrusion blending, thereby deteriorating the transparency and haze.

Korean Patent No. 1267852 discloses a resin composition containing a polyarylate resin and a polycarbonate resin and a resin composition containing spherical silica, but it is also possible to use a mixture obtained by blending polycarbonate resin and polyarylate resin at a predetermined ratio There is a problem that the compatibility is deteriorated due to the difference in refractive index as the resin and the transmittance is lowered.

U.S. Patent No. 4,388,455 discloses an ester / carbonate copolymer obtained by polymerizing an ester / carbonate oligomer prepared by mixing bisphenol A, terephthaloyl chloride and dihydric carbonate oligomer, And the interfacial polymerization process is applied, so that a large factory site is required, and the apparatus cost and operation cost are high.

Korean Patent Laid-Open Publication No. 2006-0062309 discloses a process for producing an aromatic dihydroxy compound, which comprises an ester exchange reaction between an aromatic dihydroxy compound and a carbonic acid diester compound, an ester reaction between an aromatic dihydroxy compound and a dicarboxylic acid compound, condensation polymerization, Discloses a process for producing a high molecular weight polyester carbonate resin. However, in order to crystallize a low molecular weight resin for solid phase polymerization, a high volatility and toxic organic solvent is used, In addition, expensive tin catalysts have to be used and there is a problem that a solid state polymerization process must be additionally introduced.

International Patent Publication No. WO2017-126901 discloses a thermoplastic copolymer resin obtained by copolymerizing an ester oligomer having a specific structure with a polycarbonate oligomer, but there is a problem in that each polymerization step is required in the step of obtaining each oligomer.

International Patent Publication No. WO2017-126901 discloses a method for producing a polycarbonate / polyarylate alloy or a compound by mixing polycarbonate with a polyarylate resin, but a step of polymerizing each resin is required, There arises a problem of lowering the transmittance due to the difference in refractive index between the two layers.

Accordingly, it is an object of the present invention to provide a polyester carbonate copolymer having excellent heat resistance of polyarylate and excellent processability and transparency, and a process for producing the same by a simplified process, and a molded article produced using the same.

Disclosure of the Invention In order to solve the above-described problems, the present invention provides a polymer comprising repeating units represented by the following general formula (1): And a repeating unit represented by the following formula (2).

[Chemical Formula 1]

(2)

In formulas (1) and (2), A represents a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms or an arylene group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 40 carbon atoms or a heteroaryl group having 2 to 40 carbon atoms B represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 1 to 20 carbon atoms, An unsubstituted heteroalkyl group having 1 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms and may contain nitrogen, oxygen, phosphorus, silicon, a halogen element or a metal element in its structure.

Wherein the copolymer has a glass transition temperature (Tg) of 100 to 200 ° C.

And the copolymer has a transparency (ASTM D1003) of 87% or more.

In order to solve the above-mentioned other problems, the present invention provides a compound represented by the following general formula (3): A compound represented by Formula 4 below; And a compound represented by the following general formula (5). The present invention also provides a process for producing a polyester carbonate copolymer comprising the steps of:

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the general formulas (3) and (4), R is independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, B is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms A substituted or unsubstituted C1 to C20 heteroalkylene group or a C2 to C20 heteroarylene group, and may contain nitrogen, oxygen, phosphorus, silicon, a halogen element or a metal Wherein A is a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms or an arylene group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 40 carbon atoms, or a substituted or unsubstituted arylene group having 2 to 40 carbon atoms And the nitrogen, oxygen, phosphorus, sulfur, silicon, halogen element or metal element may be contained in the structure.

The compound represented by Formula 3 is at least one selected from the group consisting of diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate and dibutyl carbonate. Carbonate copolymer of the present invention.

In addition, the compound represented by the above-mentioned general formula (4) is preferably a compound represented by the following general formula (1): diphenyl terephthalate, diphenyl isophthalate, diphenyl phthalate, diphenyl 4,4-biscyclohexanecarboxylate, diphenyl propanedioate, diphenyl butane dioate, Wherein the polyester carbonate copolymer is at least one selected from the group consisting of dibutyl phthalate, dibutyl phthalate, dibutyl phthalate, diethoxide, diphenylhexanedioate, diphenylheptanedioate, diphenyloctanedioate, diphenylnonanedioate and diphenyldecanedioate. And a manufacturing method thereof.

In addition, the compound represented by the above-mentioned general formula (5) is preferably a compound represented by the following general formula (1): ethylene glycol, 1,3-propanediol, 1,2- propanediol, 1,4- Diethylene glycol, triethylene glycol, tetraethylene glycol, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1,6-hexanediol, 4,4'-isopropylidene dicyclohexanol, Bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis Bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, Dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, 1,1- Ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis Phenyl sulfone, bis (4- Hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-2,5 Diethoxydiphenyl ether, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis Fluorine, fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, and 9,9-bis (4-hydroxy-2-methylphenyl) fluorene. Carbonate copolymer of the present invention.

The first reaction step in which the melt polycondensation reaction is carried out under reduced pressure conditions of 50 to 750 Torr and at a temperature of 150 to 250 DEG C for 0.1 to 5 hours; And a second reaction step at a reduced pressure of 10 Torr or less and at a temperature of 200 to 300 DEG C for 0.1 to 10 hours.

And the catalyst used in the melt polycondensation reaction comprises an alkali metal compound or an alkaline earth metal compound.

According to another aspect of the present invention, there is provided a molded article comprising the polyester carbonate copolymer.

The polyester carbonate copolymer according to the present invention can be produced by melt polycondensation of a specific monomer mixture so that the conventional polyarylate and polycarbonate are polymerized and blended respectively, Optical performance can be remarkably improved.

Such a polyester carbonate copolymer according to the present invention is excellent in heat resistance and transparency and can be used in a container field such as a bottle or the like, a lens for a camera lens, a finder lens or the like, a display retardation film, a diffusion sheet polarizing film, It is possible to provide materials in a wide range of fields such as window members and window pane members.

1 is a photograph of a specimen according to Example 4 and Comparative Examples 6 to 8 for visually confirming a difference in transmittance and haze in the test example of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Throughout the specification, when an element is referred to as " including " an element, it means that it can include other elements, not excluding other elements, unless specifically stated otherwise.

The inventors of the present invention have conducted studies to solve the problem that the optical performance such as the transmittance and the fogging is lowered when blending with the polycarbonate for improving the processing performance of the conventional polyarylate resin. As a result, To produce a polyester polycarbonate copolymer, it is possible to dramatically improve the optical performance as well as the processability, while achieving the same level of heat resistance without the additional blending process.

Accordingly, the present invention provides a resin composition comprising: a repeating unit represented by the following formula (1); And a repeating unit represented by the following formula (2).

[Chemical Formula 1]

(2)

In formulas (1) and (2), A represents a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms or an arylene group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 40 carbon atoms or a heteroaryl group having 2 to 40 carbon atoms B represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 1 to 20 carbon atoms, An unsubstituted heteroalkyl group having 1 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms and may contain nitrogen, oxygen, phosphorus, silicon, a halogen element or a metal element in its structure.

Hereinafter, the process for producing the polyester carbonate copolymer according to the present invention will be described in detail.

The method for producing a polyester carbonate copolymer according to the present invention comprises: A compound represented by Formula 4 below; And a compound represented by the following general formula (5).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the general formulas (3) and (4), R is independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, B is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms A substituted or unsubstituted C1 to C20 heteroalkylene group or a C2 to C20 heteroarylene group, and may contain nitrogen, oxygen, phosphorus, silicon, a halogen element or a metal Wherein A is a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms or an arylene group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 40 carbon atoms, or a substituted or unsubstituted arylene group having 2 to 40 carbon atoms And the nitrogen, oxygen, phosphorus, sulfur, silicon, halogen element or metal element may be contained in the structure.

The compound represented by the formula (4) and the compound represented by the formula (5) react to form an ester bond, and the compound represented by the formula (3) and the compound represented by the formula (5) react to form a carbonate bond.

The carbonic acid diester compound represented by Formula 3 may be at least one selected from the group consisting of diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate and dibutyl carbonate And may preferably be diphenyl carbonate.

The dicarboxylic compound represented by the formula (4) may be, for example, diphenyl terephthalate, diphenyl isophthalate, diphenyl phthalate, diphenyl 4,4-biscyclohexanecarboxylate, diphenyl propanedioate, diphenyl butanedioate , Diphenylpentanedioate, diphenylhexanedioate, diphenylheptanedioate, diphenyloctanedioate, diphenylnonanedioate, and diphenyldecanedioate, and preferably, at least one selected from the group consisting of Can be diphenyl terephthalate.

Examples of the compound represented by the formula (5) include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, Hexanediol, heptanediol, 1,6-hexanediol, 4,4'-isopropylidenedicyclohexanol, diethyleneglycol, triethyleneglycol, tetraethyleneglycol, 1,4-cyclohexanedimethanol, 2,2-bis Dihydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2- Propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2- Dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, 1 Bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) Sulfone, 2,4 Dihydroxydiphenyl sulfone, bis (4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether , 4,4'-dihydroxy-2,5-diethoxydiphenyl ether, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9- (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, and 9,9-bis , And preferably bisphenol A. < Desc / Clms Page number 3 > However, when the structure of A in formula (5) is an aromatic ring structure compound, it increases the heat resistance of the polymeric polymer but may be weak to impact, and when the structure of A is an aliphatic linear or cyclic compound, the impact strength and transparency are increased, It is preferable to appropriately introduce the aromatic ring structure and the aliphatic linear and cyclic structure within a specific range since the melt viscosity can be lowered to lower the workability somewhat.

The polyester carbonate copolymer may have a weight average molecular weight of 1,000 to 100,000, and preferably 5,000 to 50,000.

The reaction by the melt polymerization method is an ester exchange reaction between a multi-hydroxy compound, a carbonic acid diester and a dicarboxylate compound, mixing a multiple hydroxy compound, a dicarboxyl compound and a carbonic acid diester in the presence of an inert gas, To 300 ° C. The decompression degree is changed stepwise, and finally, the pressure is reduced to 1 Torr or less to remove the generated phenols from the reaction system. The reaction time is usually about 0.1 to 12 hours. Preferably, the melt polymerization according to the present invention is carried out under reduced pressure conditions of 50 to 750 Torr and at a temperature of 150 to 250 ° C for 0.1 to 5 hours; And a second reaction step carried out under reduced pressure conditions of 10 Torr or less and at a temperature of 200 to 300 DEG C for 0.1 to 10 hours.

The polyester carbonate copolymer produced through the above reaction can be produced, for example, by reacting a compound represented by the following formula (3) with diphenyl carbonate, a compound represented by formula (4) with diphenylterephthalate (DPT), a compound represented by formula (5) with bisphenol A and bisphenol fullerene, And the like.

[Chemical Formula 6]

Here, the respective components of X and Y are irregularly bonded in the repeating unit. When the amount of the aromatic compound represented by the general formula (4) and the general formula (5) is more than 70 mol% based on 100 mol% of the total amount of the compounds represented by the general formulas (3) , It may be difficult to shape the product due to overload during operation of the processing machine.

Also, when Formula 3 is applied to diphenyl carbonate, Formula 4 to diphenyl adipate (DPA), and Formula 5 to bisphenol A and 1,4-cyclohexane dimethanol (1,4-CHDM) And the like.

(7)

Here, the respective components of X and Y are irregularly bonded in the repeating unit. When the amount of the aliphatic compound such as diphenyl adipate and 1,4-cyclohexane dimethanol is more than 50 mol% based on 100 mol% of the total amount of the compounds represented by the general formulas (3) to (5) in the formula (7) It may not be easy to mold the product due to increased fluidity.

On the other hand, in the case of an aromatic compound such as diphenyl terephthalate represented by the following general formula (8), the compound corresponding to the general formula (5) may be a mixture of one aliphatic and one aromatic in a content not exceeding 50 mol% Is preferably used. Here, the respective components of X and Y are irregularly bonded in the repeating unit.

[Chemical Formula 8]

When the compound of formula (4) is an aliphatic compound such as diphenyl adipate as shown in the following formula (9), the aromatic compound such as bisphenol A, bisphenol fullerene, bisphenol Z and the like is preferably used alone or in combination of two or more thereof. Here, the respective components of X and Y are irregularly bonded in the repeating unit.

[Chemical Formula 9]

In order to accelerate the polymerization rate in the polyester carbonate polymerization process according to the present invention, a polymerization catalyst may be used. Examples of the polymerization catalyst include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide, hydroxides of alkaline earth metals such as magnesium hydroxide and calcium hydroxide, alkali metal salts such as sodium acetate and potassium acetate, A catalyst used in esterification reaction or ester exchange reaction such as earth metal salt, zinc compound, germanium compound, organic tin compound, titanium compound, zirconium compound and the like. The polymerization catalyst may be used alone or in combination of two or more. The amount of these polymerization catalysts to be used is preferably 1 × 10 ^-8 to 1 × 10 ^-2 equivalents, more preferably 1 × 10 ^-7 to 1 × 10 ^-3 equivalents, more preferably 1 × 10 ^-7 to 1 × 10 ^-3 equivalents, More preferably in the range of 1 × 10 ^-6 to 1 × 10 ^-4 equivalent.

On the other hand, a resin composition further comprising an ultraviolet absorber in the polyester carbonate copolymer according to the present invention can be considered as an embodiment of the present invention. The ultraviolet absorber means a compound that blocks ultraviolet energy or selectively absorbs ultraviolet energy to release it as another type of energy that is not harmful to the polymer, or inhibits the photoreaction, particularly the photolysis initiation reaction, of the polymer. The components or compounds that can be used are not limited.

Specific examples of the ultraviolet absorber include 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (3-tert- butyl- (2-hydroxy-3,5-bis (?,? - dimethylbenzyl) phenyl] -2H-benzo Triazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine- And mixtures of two or more species.

The ultraviolet absorber may be included in an amount of 0.0005 to 1 part by weight based on 100 parts by weight of the polyester carbonate resin. When the content of the ultraviolet absorber is within the above range, weather resistance of the resin composition and the molded article can be improved without causing bleeding of the ultraviolet absorber on the surface of the molded article and deterioration of mechanical properties of various molded articles.

In addition, the polyester carbonate resin composition of one embodiment may further include a release agent to increase the productivity at the time of extrusion and injection and to reduce the defective rate.

Examples of the release agent include higher fatty acid esters of higher fatty acids, mono- or polyhydric alcohols, natural animal waxes such as beeswax, natural plant waxes such as carnauba wax, natural petroleum waxes such as paraffin wax, natural coal waxes such as montan wax, An olefin wax, a silicone oil, an organopolysiloxane, or a mixture of two or more thereof.

Examples of the higher fatty acid ester include substituted or unsubstituted monovalent or polyvalent alcohols having 1 to 20 carbon atoms, and substituted or unsubstituted partial esters or esters of saturated fatty acids having 10 to 30 carbon atoms. Examples of the partial esters or all esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, stearic acid stearate, Propyleneglycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl lauroyl stearate, isopropyl palmitate, butyl stearate, methyl stearate, Isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, ethylene glycol distearate, and the like.

Examples of the higher fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.

The releasing agent may be used in an amount of 0.0001 to 0.01 part by weight based on 100 parts by weight of the polyester carbonate resin.

In addition, the polyester carbonate resin composition of one embodiment may further include a heat stabilizer to prevent the degradation of the molecular weight and the color of the resin molded article.

Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid and esters thereof, and specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4- -Butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tri (tert-butylphenyl) octylphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis Butyl phosphate, triethyl phosphate, (2,4-di-tert-butylphenyl) phosphite, triphenylphosphine, diphenylmonoctalkenylphosphate, dibutylphosphate, dioctylphosphate, diisopropylphosphate, Butylphenyl), dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, or a mixture of two or more thereof.

The heat stabilizer may be used in an amount of 0.0001 to 1 part by weight based on 100 parts by weight of the polyester carbonate resin. As the stabilizer is used in the above amount, the molecular weight of the resin and discoloration of the resin can be prevented without causing bleeding of the additive.

In addition, the polyester carbonate resin composition of one embodiment may further include a conventionally known antioxidant.

Specific examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, tri Bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3-hydroxyphenyl) propionate, pentaerythritol tetrakis Butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert- ) Benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert- Diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, (2,4-di-tert-butylphenyl) 4'-biphenylene diphosphinic acid tetrakis (2,4-di-tert- 5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane, or a mixture of two or more thereof.

The antioxidant may be used in an amount of 0.0001 to 1 part by weight based on 100 parts by weight of the polyester carbonate resin.

On the other hand, the polyester carbonate resin composition of one embodiment may further include a polymer resin other than the polyester carbonate resin for the purpose of further improving and adjusting molding processability and various physical properties.

Specifically, the polyester carbonate resin composition of one embodiment may further include at least one other polymer resin selected from the group consisting of polyester resin, polyether, polyamide, polyolefin, and polymethyl methacrylate. At this time, the other polymer resin may be included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the polyester carbonate resin.

The production of the polyester carbonate resin composition according to the present invention is not particularly limited, and any method or apparatus conventionally used in the production of a polymer resin composition or the like can be used without any limitations, but a melt polymerization method can be preferably used .

That is, the polyester carbonate resin composition of one embodiment may be prepared by melt-kneading the respective components contained therein. As a device used for the melt kneading, a Banbury mixer, a kneading roll, an extruder and the like can be given. Among them, an extruder is preferable in terms of kneading efficiency, and a multiaxial extruder such as a twin screw extruder is preferable.

The resin composition obtained as described above can be produced in the form of pellets and then used in the production of various products by injection molding. In such injection molding, injection molding, injection press molding, gas assist injection molding, foam molding (including injection of supercritical fluid), insert molding, A molded product can be obtained by using an injection molding method such as die coating molding, heat insulating mold molding, rapid heating cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The molding can be either a cold runner type or a hot runner type.

The resin composition may also be used in the form of various shaped extrusion molded articles, sheets or films by extrusion molding. In addition, inflation, calendering, casting, and the like can be used for forming sheets and films. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation.

The resin composition may be formed into a molded article by rotary molding or blow molding. By the molding process, a molded article having transparency and excellent in designability can be obtained.

According to another embodiment of the present invention, a resin molded article comprising the polyester carbonate resin composition may be provided. The resin molded article means an article obtained by molding the polyester carbonate resin composition of the embodiment described above.

The resin molded article is preferably transparent depending on the properties required in the field of use. The transparency of such a resin molded article can be evaluated by the total light transmittance in the visible light region of the resin molded article, and it is preferable that the visible light transmittance is high. Specifically, the resin molded article of the embodiment may have visible light transmittance of 50% or more, or 50 to 99% at a thickness of 3 mm.

The specific use of the resin molded article is not limited, and may be applied to a transparent film, a sheet, a bottle and a container, a lens such as a camera lens and a finder lens, a retardation film for display, a diffusion sheet, a polarizing film, , Construction window members, and the like.

Hereinafter, a specific embodiment of the present invention will be described. The abbreviations and the sources of the compounds used in the description of the examples are as follows.

- DPC: diphenyl carbonate (Lotte Chemical)

- DPT: diphenyl terephthalate (Samwoo High Tech)

- DPA: diphenyl adipate (Samwoo High Tech)

- BPA: bisphenol A (Kumho P & B)

- BP-FL: Bisphenol Fullerene (Samwoo High Tech)

- BPZ: Bisphenol Z (Samwoo High Tech)

- CHDM: 1,4-cyclohexanedimethanol, Sigma Aldrich)

- PAR: Polyarylate (U-polymer, 100%, UNITIKA)

- PC: Polycarbonate (PC-1600, Lotte Chemical)

Example 1

31.7 parts by weight (0.175 mol) of DPC, 20.2 parts by weight (0.075 mol) of DPT, 48.1 parts by weight (0.25 mol) of BPA and 5 × 10 ^-6 equivalents of cesium hydroxide as a catalyst were placed in a 1 L reactor, As the first step process, the reactor temperature was heated to 180 캜 and, if possible, the raw materials were melted while stirring. When it was confirmed that it was completely melted, the temperature was raised to 200 DEG C for 5 minutes, and the pressure inside the reactor was reduced from normal pressure to 300 Torr. The entire reaction vessel was maintained at 200 占 폚 for 30 minutes, and the generated phenol was removed from the reactor while the inner pressure was reduced to 100 Torr for 10 minutes while raising the temperature to 230 占 폚 for 10 minutes. After maintaining the entire reaction vessel at 230 占 폚 for 30 minutes, the pressure in the reaction tank was reduced to 50 Torr and the temperature of the reaction tank was raised to 250 占 폚 for 20 minutes to remove the generated phenol from the reaction vessel Respectively. When the torque of the stirrer rises, the reactor is heated up to 290 占 폚 for 20 minutes, and the pressure in the reaction vessel is lowered to 1 Torr or less in order to remove additional phenol. After reaching a predetermined stirring torque, the reaction was terminated and the resulting reaction product was taken to prepare a copolymer specimen and analyzed.

Example 2

The procedure of Example 1 was repeated except that 23.1 parts (0.15 mol) of DPC, 22.8 parts (0.1 mol) of DPT, 16.4 parts (0.1 mol) of BPA and 37.7 parts (0.15 mol) The copolymers were prepared in the same manner.

Example 3

Example 1 was repeated except that in Example 1, DPC was adjusted to 26.8 parts (0.175 mol), DPT 17.1 parts (0.075 mol), BPA 12.2 parts (0.075 mol) and BPFL 43.9 parts (0.175 mol) A polyester copolymer was prepared in the same manner.

Example 4

The procedure of Example 1 was repeated except that 17.0 parts (0.1 mol) of DPC, 38.0 parts (0.15 mol) of DPT, 27.8 parts (0.1 mol) of BPFL and 17.2 parts (0.15 mol) The copolymers were prepared in the same manner.

Example 5

Except that 14.9 parts by weight of DPC (0.1 mol), 31.2 parts by weight of DPA (0.15 mol), 48.8 parts by weight of BPFL (0.2 mol) and 5.0 parts by weight of CHDM (0.05 mol) Lt; / RTI >

Example 6

Copolymers were prepared in the same manner as in Example 1, except that 16.1 parts by weight (0.1 mol) of DPC, 33.6 parts by weight (0.15 mol) of DPA and 50.3 parts by weight (0.25 mol) of BPZ were used in Example 1.

Example 7

Example 1 was repeated except that DPC was adjusted to 10.8 parts by weight (0.075 mol), DPT 37.4 parts by weight (0.175 mol), BPFL 47.0 parts by weight (0.2 mol) and CHDM 4.8 parts by weight (0.05 mol) The copolymers were prepared in the same manner.

Comparative Example 1

A copolymer was prepared in the same manner as in Example 1 except that 58.2 parts by weight (0.25 mol) of DPT and 41.8 parts by weight (0.25 mol) of BPA were used in Example 1.

Comparative Example 2

A copolymer was prepared in the same manner as in Example 1 except that 59.8 parts by weight (0.25 mol) of DPC and 40.3 parts by weight (0.25 mol) of CHDM were used in Example 1.

Comparative Example 3

A copolymer was prepared in the same manner as in Example 1 except that 68.8 parts by weight (0.25 mol) of DPT and 31.2 parts by weight (0.25 mol) of CHDM were used in Example 1.

Comparative Example 4

A commercially available polycarbonate resin (PC-1600, Lotte Chemical) was prepared.

Comparative Example 5

A commercial polyarylate resin (U-100, UNITIKA) was prepared.

Comparative Example 6

30 parts by weight of commercial polyarylate (U-100, UNITIKA) and 70 parts by weight of commercial polycarbonate (PC-1600, Lotte Chemical) were melt-kneaded in a temperature range of 310 to 340 占 폚 using a biaxial extruder To prepare a pellet-form compound resin.

Comparative Example 7

In Comparative Example 6, a compound resin was prepared in the same manner as in Comparative Example 6, except that 50 parts by weight of polyarylate and 50 parts by weight of polycarbonate were used.

Comparative Example 8

In Comparative Example 6, a compound resin was prepared in the same manner as in Comparative Example 6, except that 70 parts by weight of polyarylate and 30 parts by weight of polycarbonate were used.

Comparative Example 9

In Comparative Example 6, a compound resin was prepared in the same manner as in Comparative Example 6, except that 90 parts by weight of polyarylate and 10 parts by weight of polycarbonate were used.

Test Example

The glass transition temperature, the transmittance and the haze of the resin prepared or prepared according to the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1 below. At this time, injection molding specimens could not be obtained as the copolymers according to Comparative Examples 1, 2, 3 and 5. On the other hand, a photograph of a test piece according to Example 4 and Comparative Examples 6 to 8 (Figs. 1 (a) to 1 (d), respectively) is shown in Fig. 1 to visually confirm the transmittance and haze difference.

(1) Glass transition temperature (Tg)

The sample was heated to a temperature elevation rate of 10 占 폚 / min using about 10 mg of a sample in a differential scanning calorimeter (Q200, TA Instruments), and a straight line extending from the low temperature side to the high temperature side in accordance with ASTM D3418, The extrapolated glass transition onset temperature Tg, which is the temperature at the intersection of the line at the point where the slope of the curve of the step-change portion of the transition becomes maximum, is obtained.

(2) Total light transmittance and haze

Injection molded at a temperature of 230 to 300 占 폚 at a width of 50 mm, a length of 70 mm and a thickness of 3.0 mm using a 25-ton injection molding machine manufactured by Dongshin Hydraulic Co., Ltd. The total light transmittance and haze of the specimen obtained in accordance with ASTM D 1003 were measured using a measuring instrument of NDH-5000 model manufactured by Nippon Denshoku.

Referring to Table 1 and FIG. 1, in the case of producing a polyester carbonate copolymer by melt polycondensation of a specific monomer mixture according to the present invention in a single process, the polyarylate and the polycarbonate were polymerized, respectively, The haze is markedly reduced and the transmittance is higher than that of the resin as a whole. However, when the formula (4) and the formula (5) are composed of an aromatic compound, the permeability and haze may be somewhat lowered when the content is excessive (see Example 7).

The glass transition temperature is similar to that of the polycarbonate / polyarylate (PC / PAR) alloy resin, and can be sufficiently overcome by adjustment of the monomer component. However, if the contents of aromatic and aliphatic components are excessively biased, it may be difficult to process due to high heat resistance or viscosity, so proper distribution according to the application should be made.

The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning, range, and equivalence of the claims are included in the scope of the present invention Should be interpreted.

Claims (10)

A repeating unit represented by the following formula (1); And a repeating unit represented by the following formula (2): < EMI ID =
[Chemical Formula 1]

(2)

In formulas (1) and (2), A represents a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms or an arylene group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 40 carbon atoms or a heteroaryl group having 2 to 40 carbon atoms B represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 1 to 20 carbon atoms, An unsubstituted heteroalkyl group having 1 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms and may contain nitrogen, oxygen, phosphorus, silicon, a halogen element or a metal element in its structure. The method according to claim 1,
Wherein the copolymer has a glass transition temperature (Tg) of 100 to 200 占 폚. The method according to claim 1,
Wherein the copolymer has a transmittance (ASTM D1003) of 87% or more. A compound represented by the following formula (3); A compound represented by Formula 4 below; And a compound represented by the following general formula (5): (A)
(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the general formulas (3) and (4), R is independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, B is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms A substituted or unsubstituted C1 to C20 heteroalkylene group or a C2 to C20 heteroarylene group, and may contain nitrogen, oxygen, phosphorus, silicon, a halogen element or a metal Wherein A is a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms or an arylene group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 40 carbon atoms, or a substituted or unsubstituted arylene group having 2 to 40 carbon atoms And the nitrogen, oxygen, phosphorus, sulfur, silicon, halogen element or metal element may be contained in the structure. 5. The method of claim 4,
The compound represented by Formula 3 is at least one selected from the group consisting of diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate and dibutyl carbonate. ≪ / RTI > 5. The method of claim 4,
The compound represented by the general formula (4) may be at least one selected from the group consisting of diphenyl terephthalate, diphenyl isophthalate, diphenyl phthalate, diphenyl 4,4-biscyclohexanecarboxylate, diphenyl propanedioate, diphenyl butanedioate, Wherein the polyester resin is at least one member selected from the group consisting of diphenylmethane diisocyanate, diphenylhexanedioate, diphenylheptanedioate, diphenyloctanedioate, diphenylnonanedioate and diphenyldecanedioate. Way. 5. The method of claim 4,
The compound represented by the general formula (5) may be at least one selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 4,4'-isopropylidenedicyclohexanol, diethylene glycol, triethylene glycol, tetraethylene glycol, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy- Bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) Dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, 1,1- , 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, Sulfone, bis (4- 4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-2,5- Diethoxydiphenyl ether, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy- (4-hydroxyphenyl) fluorene, and 9,9-bis (4-hydroxy-2-methylphenyl) fluorene. ≪ / RTI > 5. The method of claim 4,
Wherein the melt polycondensation reaction is conducted at a reduced pressure of 50 to 750 Torr and at a temperature of 150 to 250 ° C for 0.1 to 5 hours; And a second reaction step at a reduced pressure of 10 Torr or less and at a temperature of 200 to 300 占 폚 for 0.1 to 10 hours. 5. The method of claim 4,
Wherein the catalyst used in the melt polycondensation reaction comprises an alkali metal compound or an alkaline earth metal compound. A molded article comprising the polyester carbonate copolymer according to any one of claims 1 to 3.

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