KR102200878B1 - Polyester-carbonate copolymer and method for preparing same and molded articl by using same - Google Patents

Abstract

[화학식 2]

화학식 1 및 2에서, A는 치환 또는 비치환된 탄소수 1 내지 40의 알킬렌기 또는 탄소수 6 내지 40의 아릴렌기, 치환 또는 비치환된 탄소수 1 내지 40의 헤테로 알킬렌기 또는 탄소수 2 내지 40의 헤테로 아릴렌기이고, 구조내에 질소, 산소, 인, 황, 규소, 할로겐 원소 또는 금속 원소가 포함될 수 있고, B는 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기 또는 탄소수 6 내지 20의 아릴렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로 알킬기 또는 탄소수 2 내지 20의 헤테로 아릴렌기이고, 구조내에 질소, 산소, 인, 황, 규소, 할로겐 원소 또는 금속 원소가 포함될 수 있다.Disclosed is a polyester carbonate copolymer having excellent heat resistance of polyarylate and excellent processability and transparency. The present invention is a repeating unit represented by the following formula (1); And it provides a polyester carbonate copolymer comprising; and a repeating unit represented by the following formula (2).
[Formula 1]

[Formula 2]

In Formulas 1 and 2, 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 heteroaryl having 2 to 40 carbon atoms. Is a ene group, nitrogen, oxygen, phosphorus, sulfur, silicon, a halogen element or a metal element may be included in the structure, and B is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, substituted or It is an unsubstituted C1-C20 heteroalkyl group or a C2-C20 heteroarylene group, and nitrogen, oxygen, phosphorus, sulfur, silicon, a halogen element, or a metal element may be included in a structure.

Description

Polyester carbonate copolymer and manufacturing method and molded article using the same {POLYESTER-CARBONATE COPOLYMER AND METHOD FOR PREPARING SAME AND MOLDED ARTICL BY USING SAME}

The present invention relates to a polyester carbonate copolymer and a method of manufacturing the same, and more particularly, to a polyester carbonate copolymer having high transparency and high heat resistance, and a method of manufacturing the same.

Polyarylate (PAR) resin is generally produced by interfacial polymerization of bisphenol A and terephthaloyl chloride (TPC), and has excellent heat resistance and is transparent. However, due to its high heat resistance, processability is very inferior to other engineering plastic resins.

In order to improve the processing performance of such polyarylate resins, transparent engineering plastic resins having excellent processing performance such as polycarbonate (PC) are blended in a compound form and used. However, since the refractive indices of polycarbonate and polyarylate are similar but not the same, optical performances such as transmittance and haze when used in combination are lower than those of the original resins, and polycarbonate and polyarylate are synthesized respectively. After that, it must go through a two-step process of blending at a certain ratio.

Japanese Unexamined Patent Application Publication No. 2009-167291 discloses a polyarylate composed of bisphenol having a cyclohexane ring structure, bisphenol having an isopropyriden skeleton, and aromatic dicarboxylic acid, but it is harmful due to the use of a chlorine-based compound. , The interfacial polymerization process is applied, so the equipment cost and operation cost are high, and the resulting copolymer resin has poor processability, making it difficult to process such as extrusion and injection molding, and it has a problem that it must be dissolved in a solvent and used only in the form of a film.

Korean Patent Publication No. 2015-0081989 discloses a resin composition in which polycarbonate and polyarylate are mixed, but each resin must be individually polymerized and a compound manufacturing method using an extruder must be applied. Compatibility is poor, and polyarylate causes color change due to high temperature during extrusion blending, resulting in a problem in that transmittance and haze are deteriorated.

Korean Patent No. 1278572 discloses a resin containing a polyarylate resin and a polycarbonate resin, and a resin composition containing spherical silica, but a mixture of polycarbonate resin and polyarylate resin each product is blended at a certain ratio. As a resin, there is a problem that the transmittance decreases due to poor compatibility due to the difference in refractive index.

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, but there is a hazard due to the use of chlorine-based compounds. In addition, since the interfacial polymerization process is applied, a large factory site is required, and equipment and operation costs are high.

Korean Patent Laid-Open Publication No. 2006-0062309 discloses a transesterification reaction of an aromatic dihydroxy compound and a carbonic acid diester compound, and esterification, condensation polymerization, crystallization and solid phase polymerization of an aromatic dihydroxy compound and a dicarboxylic acid compound. Although a method of manufacturing a high molecular weight polyester carbonate resin is disclosed, a high volatility and toxic organic solvent is used for crystallization of a low molecular weight resin for solid phase polymerization, and additional equipment and operating costs are required for the treatment thereof, and catalysts In addition, there is a problem in that an expensive tin catalyst must be used and a solid phase polymerization process must be additionally introduced.

International 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 process is required in the step of obtaining each oligomer.

International Publication No. WO2017-126901 discloses a method of preparing a polycarbonate/polyarylate alloy or compound by mixing polycarbonate with a polyarylate resin, but a process of polymerizing each resin is required, and each resin There is a problem of lowering the transmittance due to the difference in refractive index of.

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

In order to solve the above problems, the present invention, a repeating unit represented by the following formula (1); And it provides a polyester carbonate copolymer comprising; and a repeating unit represented by the following formula (2).

[Formula 1]

[Formula 2]

In Formulas 1 and 2, 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 heteroaryl having 2 to 40 carbon atoms. Is a ene group, nitrogen, oxygen, phosphorus, sulfur, silicon, a halogen element or a metal element may be included in the structure, and B is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, substituted or It is an unsubstituted C1-C20 heteroalkyl group or a C2-C20 heteroarylene group, and nitrogen, oxygen, phosphorus, sulfur, silicon, a halogen element, or a metal element may be included in a structure.

In addition, the copolymer provides a polyester carbonate copolymer, characterized in that the glass transition temperature (Tg) is 100 ~ 200 ℃.

In addition, the copolymer provides a polyester carbonate copolymer, characterized in that the transmittance (ASTM D1003) is 87% or more.

In order to solve the above other problems, the present invention is a compound represented by the following formula (3); A compound represented by the following formula (4); And it provides a method for producing a polyester carbonate copolymer comprising the step of melt-condensation polymerization of a monomer mixture comprising a compound represented by the following formula (5).

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 and 4, R is each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and in Formula 4, B is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms An arylene group or an arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms, and nitrogen, oxygen, phosphorus, sulfur, silicon, halogen element or metal in the structure An element may be included, and in Formula 5, 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 2 to 40 carbon atoms. Is a heteroarylene group of, and may contain nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements or metal elements in the structure.

In addition, the compound represented by Formula 3 is one or more selected from the group consisting of diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. It provides a carbonate copolymer preparation method.

In addition, the compound represented by Formula 4 is diphenyl terephthalate, diphenyl isophthalate, diphenyl phthalate, diphenyl 4,4-biscyclohexane carboxylate, diphenyl propanedioate, diphenyl butanedioate, diphenyl pentane Polyester carbonate copolymer, characterized in that it is at least one selected from the group consisting of dioate, diphenyl hexanedioate, diphenyl heptanedioate, diphenyl octanedioate, diphenyl nonanedioate and diphenyl decanedioate Provides a manufacturing method.

In addition, the compound represented by Formula 5 is ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol , 1,6-hexanediol, 4,4'-isopropylidenedicyclohexanol, diethylene glycol, triethylene glycol, tetraethylene glycol, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) , 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4- Hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane , 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl) Ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydi Phenylsulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxy-3,3'-dichlorodiphenylether, 4,4'- Dihydroxy-2,5-diethoxydiphenyl ether, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy) -2-methyl)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-2-methylphenyl)fluorene It provides a method for producing a polyester carbonate copolymer characterized in that the above.

In addition, the melt-condensation polymerization reaction is performed under a reduced pressure condition of 50 to 750 Torr and a temperature of 150 to 250°C for 0.1 to 5 hours; And a second reaction step performed for 0.1 to 10 hours at a reduced pressure condition of 10 Torr or less and a temperature of 200 to 300° C.; it provides a method for producing a polyester carbonate copolymer.

In addition, the catalyst used in the melt-condensation polymerization reaction provides a method comprising an alkali metal compound or an alkaline earth metal compound.

In order to solve the above another problem, the present invention provides a molded article comprising the polyester carbonate copolymer.

The polyester carbonate copolymer according to the present invention is prepared by melt-condensation polymerization of a specific monomer mixture, so that it has the same level of heat resistance without an additional blending process compared to the conventional resin obtained by polymerizing and mixing polyarylate and polycarbonate. Optical performance can be remarkably improved.

Since the polyester carbonate copolymer according to the present invention has excellent heat resistance and transparency, it is used in the field of containers such as bottles, lens applications such as camera lenses and finder lenses, display retardation films, diffusion sheet polarizing films, optical disks, optical materials, optical parts, and construction. It is possible to provide materials for a wide range of fields such as window members and vehicle window members.

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

Hereinafter, a preferred embodiment of the present invention will be described in detail. In describing the present invention, when it is determined that a detailed description of a related known technology may obscure the subject matter of the present invention, a detailed description thereof will be omitted. Throughout the specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components, unless otherwise stated.

In order to improve the processing performance of the conventional polyarylate resin, the present inventors have repeatedly studied to solve the problem that the optical performance such as transmittance and haze is deteriorated when blending with polycarbonate. As a result, a specific monomer mixture is melted and condensed. In the case of manufacturing a polyester polycarbonate copolymer, it was discovered that it was possible to dramatically improve optical performance along with processability while having the same level of heat resistance without an additional blending process.

Thus, the present invention is a repeating unit represented by the following formula (1); And a repeating unit represented by the following Chemical Formula 2;

[Formula 1]

[Formula 2]

In Formulas 1 and 2, 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 heteroaryl having 2 to 40 carbon atoms. Is a ene group, nitrogen, oxygen, phosphorus, sulfur, silicon, a halogen element or a metal element may be included in the structure, and B is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, substituted or It is an unsubstituted C1-C20 heteroalkyl group or a C2-C20 heteroarylene group, and nitrogen, oxygen, phosphorus, sulfur, silicon, a halogen element, or a metal element may be included in a structure.

Hereinafter, it will be described in detail through the manufacturing process of the polyester carbonate copolymer according to the present invention.

The method for preparing a polyester carbonate copolymer according to the present invention comprises a compound represented by the following formula (3); A compound represented by the following formula (4); And a step of melt-condensation polymerization of a monomer mixture including a compound represented by the following Chemical Formula 5.

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 and 4, R is each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and in Formula 4, B is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms An arylene group or an arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms, and nitrogen, oxygen, phosphorus, sulfur, silicon, halogen element or metal in the structure An element may be included, and in Formula 5, 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 2 to 40 carbon atoms. Is a heteroarylene group of, and may contain nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements or metal elements in the structure.

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

Here, the carbonate diester compound represented by Formula 3 is, for example, one or more selected from the group consisting of diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. It may be, preferably diphenyl carbonate.

In addition, the dicarboxyl compound represented by Formula 4 is, for example, diphenyl terephthalate, diphenyl isophthalate, diphenyl phthalate, diphenyl 4,4-biscyclohexane carboxylate, diphenyl propanedioate, diphenyl butanedioate. , Diphenyl pentanedioate, diphenyl hexanedioate, diphenyl heptanedioate, diphenyl octanedioate, diphenyl nonanedioate and diphenyl decanedioate may be at least one selected from the group consisting of, and preferably May be diphenyl terephthalate.

In addition, the compound represented by Formula 5 is, for example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5- Heptanediol, 1,6-hexanediol, 4,4'-isopropylidenedicyclohexanol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-cyclohexanedimethanol, 2,2-bis( 4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl )Propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2, 2-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1 ,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl) Sulfone, 2,4'-dihydroxy diphenylsulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxy-3,3' -Dichlorodiphenylether, 4,4'-dihydroxy-2,5-diethoxydiphenylether, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9- Bis(4-(2-hydroxyethoxy-2-methyl)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-2-methylphenyl) ) It may be one or more selected from the group consisting of fluorene, preferably bisphenol A. However, in the case where the structure of A is an aromatic cyclic compound in Formula 5, the heat resistance of the polymerized polymer is increased, but it may be weak against impact, and when the structure of A is an aliphatic linear or cyclic compound, the impact strength and transparency are increased, but heat resistance decreases. It is also preferable to appropriately introduce an aromatic cyclic structure and an aliphatic linear and cyclic structure within a specific range because the melt viscosity may be lowered to slightly decrease the processability.

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

The reaction by the melt polymerization method is a transesterification reaction of a multi-hydroxy group compound with a diester carbonate and a dicarboxylate compound. A multi-hydroxy group compound, a dicarboxyl compound, and a diester carbonate are mixed in the presence of an inert gas, and usually 100 under reduced pressure. Reaction at ~300 ℃. The degree of decompression is changed step by step, and finally, the phenols produced are removed from the reaction system by 1 Torr or less. The reaction time is usually about 0.1 to 12 hours. Preferably, the melt polymerization according to the present invention is performed under a reduced pressure condition of 50 to 750 Torr and a first reaction step performed for 0.1 to 5 hours at a temperature of 150 to 250°C; And a second reaction step performed for 0.1 to 10 hours at a reduced pressure condition of 10 Torr or less and a temperature of 200 to 300°C.

When the polyester carbonate copolymer prepared through the above reaction is applied, for example, Formula 3 as diphenyl carbonate, Formula 4 as diphenyl terephthalate (DPT), and Formula 5 as bisphenol A and bisphenol fullerene, the following Formula 6 It will contain repeating units such as

[Formula 6]

Here, each component of X and Y is irregularly combined within the repeating unit. When formula 4 and formula 5 are composed of an aromatic compound as shown in formula 6, the amount of the aromatic compound of formula 4 and formula 5 exceeds 70 mol% based on 100 mol% of the total amount of the compound corresponding to formula 3 to formula 5 In this case, it has high heat resistance, but it may be difficult to mold the product due to overload when operating the processing equipment.

In addition, when formula 3 is applied to diphenyl carbonate, formula 4 to diphenyl adipate (DPA), and formula 5 to bisphenol A and 1,4-cyclohexanedimethanol (1,4-CHDM), the following formula 7 It will contain repeating units such as

[Formula 7]

Here, each component of X and Y is irregularly combined within the repeating unit. If the amount of aliphatic compounds such as diphenyl adipate and 1,4-cyclohexanedimethanol exceeds 50 mol% based on 100 mol% of the total usage of the compounds corresponding to formulas 3 to 5 in formula 7, heat resistance is low. It may not be easy to mold a product due to its increased fluidity.

On the other hand, when an aromatic compound such as diphenyl terephthalate in Formula 4 as shown in Formula 8 below, the compound corresponding to Formula 5 is a mixture of one aliphatic and one aromatic compound within a range that does not exceed 50 mol% of the total. It is preferable to use. Here, each component of X and Y is irregularly combined within the repeating unit.

[Formula 8]

In addition, when Formula 4 is an aliphatic compound such as diphenyl adipate as shown in Formula 9 below, Formula 5 is preferably used alone or in combination of two or more aromatic compounds such as bisphenol A, bisphenol fullerene, and bisphenol Z. Here, each component of X and Y is irregularly combined within the repeating unit.

[Formula 9]

In the polyester carbonate polymerization process according to the present invention, a polymerization catalyst may be used to speed up the polymerization rate. 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, and alkalis such as calcium acetate. Examples of catalysts commonly used in esterification and transesterification reactions such as earth metal salts, zinc compounds, germanium compounds, organotin compounds, titanium compounds, and zirconium compounds are mentioned. The polymerization catalyst may be used alone, or two or more types may be used in combination. The amount of these polymerization catalysts used is preferably 1×10 ^-8 to 1×10 ^-2 equivalent, more preferably 1×10 ^-7 to 1×10 ^-3 equivalent, more preferably 1×10 ^-8 to 1×10 ^-2 equivalent, based on 1 mol of dihydric phenol of the raw material. More preferably, it is selected from the range of 1×10 ^-6 to 1×10 ^-4 equivalents.

On the other hand, a resin composition further comprising an ultraviolet absorber in the polyester carbonate copolymer according to the present invention may be considered as an embodiment of the present invention. The ultraviolet absorber refers to a compound that blocks ultraviolet energy or selectively absorbs ultraviolet energy and releases it as another form of energy that does not harm the polymer, or inhibits the photoreaction of the polymer, especially the photolysis initiation reaction. Components or compounds that can be used may be used without great limitation.

Specific examples of the ultraviolet absorber include 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5 -Chlorobenzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzo Triazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one) or 2 thereof Mixtures of more than one kind are mentioned.

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, it is possible to improve the weather resistance of the resin composition and the molded article without causing bleeding of the ultraviolet absorber to the surface of the molded article and deterioration of mechanical properties of various molded articles.

In addition, the polyester carbonate resin composition of the embodiment may further include a release agent to increase productivity during extrusion and injection and to reduce defect rates.

Examples of the release agent include higher fatty acids, higher fatty acid esters of monohydric 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, Olefin wax, silicone oil, organopolysiloxane, or mixtures of two or more thereof.

Examples of the higher fatty acid ester include a substituted or unsubstituted monohydric or polyhydric alcohol having 1 to 20 carbon atoms, and a partial ester or ester of a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms. As the partial or all esters of the monohydric or polyhydric alcohol and saturated fatty acid, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearate monosorbate, stearyl stearate, behenic acid monoglyceride Ride, behenyl behenyl, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyllau Rate, 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, and behenic acid.

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

In addition, the polyester carbonate resin composition of the embodiment may further include a heat stabilizer to prevent a decrease in molecular weight or color deterioration of the resin molded article.

Examples of the heat stabilizer include phosphorous acid, phosphoric acid, aphosphonic acid, phosphonic acid, and esters thereof, and specifically, triphenylphosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert -Butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite Pite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite, 2,2-methylenebis(4,6-di -tert-butylphenyl) octylphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tri Butyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4'-biphenylenediphosphinic acid tetrakis (2 ,4-di-tert-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. By using the stabilizer in the above amount, it is possible to prevent the molecular weight decrease or discoloration of the resin without causing bleeding of the additive.

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

Specific examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, tri Ethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl -4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3 ,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl )Benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate -Diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 4,4'-biphenylenediphosphinic acid tetrakis (2,4-di-tert- Butylphenyl), 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-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 the embodiment may further include a polymer resin other than the polyester carbonate resin for the purpose of further improvement and adjustment of molding processability or various physical properties.

Specifically, the polyester carbonate resin composition of the embodiment may further include one or more other polymer resins selected from the group consisting of polyester-based resins, polyethers, polyamides, polyolefins and polymethyl methacrylate. In this case, the other polymer resin may be further included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the polyester carbonate resin.

The preparation of the polyester carbonate resin composition according to the present invention is not particularly limited, and a method or apparatus commonly used for preparing a polymer resin composition may be used without any other limitation, but a melt polymerization method may be preferably used. .

That is, the polyester carbonate resin composition of the embodiment may be prepared by melt-kneading each component contained therein. As an apparatus used for the melt-kneading, a Banbury mixer, a kneading roll, an extruder, and the like can be mentioned. Among them, an extruder is preferable from the viewpoint of kneading efficiency, and a multi-screw extruder such as a twin-screw extruder is preferable.

After the resin composition obtained as described above is manufactured in the form of pellets, it can be used for manufacturing various products by injection molding. In such injection molding, not only the usual molding method, but also injection compression molding, injection press molding, gas assisted injection molding, foam molding (including those by injection of supercritical fluid), insert molding, in-mold depending on the purpose as appropriate. Molded products can be obtained using injection molding methods such as de-coating molding, thermal insulation mold molding, rapid heating cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. For molding, either a cold runner method or a hot runner method can be selected.

In addition, the resin composition may be used in the form of various release extrusion molded products, sheets, films, etc. by extrusion molding. In addition, an inflation method, a calender method, a casting method, or the like can be used for forming a sheet or film. Further, it is also possible to form a heat-shrinkable tube by applying a specific stretching operation.

Further, it is also possible to make the resin composition into a molded article by rotational molding or blow molding. By the above molding process, a molded article having transparency and excellent designability can be obtained.

Meanwhile, according to another embodiment of the present invention, a resin molded article including the prepared polyester carbonate resin composition may be provided. The resin molded article means an article obtained by molding the polyester carbonate resin composition of the above-described embodiment.

It is preferable that the resin molded article is transparent depending on the properties required in the field to be used. 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 total light transmittance of visible light is high. Specifically, the resin molded article of the embodiment may have a total visible light transmittance of 50% or more, or 50 to 99% at a thickness of 3 mm.

The specific use of the resin molded product is not limited, and the use of lenses such as transparent films, sheets, bottles and containers, camera lenses, and finder lenses, retardation films for displays, diffusion sheets, polarizing films, optical disks, optical materials, optical parts , It can be used as a window member for construction.

Hereinafter, a specific example according to the present invention will be described. The symbols and sources of the compounds used in the description of the examples are as follows.

-DPC: diphenyl carbonate (Lotte Chemical)

-DPT: diphenyl terephthalate (Samwoo Hi-Tech)

-DPA: diphenyl adipate (Samwoo Hi-Tech)

-BPA: Bisphenol A (Kumho P&B)

-BP-FL: Bisphenol fluorene (Samwoo Hi-Tech)

-BPZ: Bisphenol Z (Samwoo Hi-Tech)

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

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

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

Example 1

DPC 31.7 parts by weight (0.175 mol), DPT 20.2 parts by weight (0.075 mol), BPA 48.1 parts by weight (0.25 mol), and cesium hydroxide 5 × 10 ^-6 equivalents as a catalyst were added to a 1 L glass reactor, and the reaction was carried out under a nitrogen atmosphere. As a first step process, the reaction bath temperature was heated to 180° C. 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° 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° C. for 30 minutes, and the internal pressure was reduced to 100 Torr for 10 minutes while increasing to 230° C. for 10 minutes to remove the generated phenol from the reactor. After maintaining the entire reaction vessel at 230°C for 30 minutes, as a second step process, the pressure in the reaction vessel is reduced to 50 Torr, the temperature of the reaction vessel is increased to 250°C for 20 minutes, and the generated phenol is discharged out of the reaction vessel to remove it. I did. When the torque of the stirrer rises, the reactor was heated up to 290° C. for 20 minutes, and the pressure in the reaction vessel reached 1 Torr or less in order to remove additional phenol generated. After reaching the predetermined stirring torque, the reaction was terminated, and the produced reaction product was taken to prepare a copolymer specimen and analyzed.

Example 2

Example 1 and Example 1 except that in Example 1, DPC 23.1 parts by weight (0.15 mol), DPT 22.8 parts by weight (0.1 mol), BPA 16.4 parts by weight (0.1 mol) and BPFL 37.7 parts by weight (0.15 mol) A copolymer was prepared in the same way.

Example 3

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

Example 4

Example 1 and Example 1 except that in Example 1, DPC 17.0 parts by weight (0.1 mol), DPT 38.0 parts by weight (0.15 mol), BPFL 27.8 parts by weight (0.1 mol) and CHDM 17.2 parts by weight (0.15 mol) A copolymer was prepared in the same way.

Example 5

DPC 14.9 parts by weight (0.1 mol), DPA 31.2 parts by weight (0.15 mol), BPFL 48.8 parts by weight (0.2 mol) and CHDM 5.0 parts by weight (0.05 mol), except for the same method as in Example 1 The coalescence was prepared.

Example 6

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

Example 7

Example 1 and Example 1, except that DPC 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) A copolymer was prepared in the same way.

Comparative Example 1

In Example 1, a copolymer was prepared in the same manner as in Example 1, except that DPT was adjusted to 58.2 parts by weight (0.25 mol) and BPA 41.8 parts by weight (0.25 mol).

Comparative Example 2

In Example 1, a copolymer was prepared in the same manner as in Example 1, except that DPC was adjusted to 59.8 parts by weight (0.25 mol) and CHDM 40.3 parts by weight (0.25 mol).

Comparative Example 3

In Example 1, a copolymer was prepared in the same manner as in Example 1, except that DPT was adjusted to 68.8 parts by weight (0.25 mol) and CHDM 31.2 parts by weight (0.25 mol).

Comparative Example 4

A commercial 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) using a twin screw extruder (φ26mm, TEM-26SS, Toshiba) in a temperature range of 310 to 340℃ Kneaded at to prepare a compound resin in the form of a pellet.

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 adjusted.

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 adjusted.

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 adjusted.

Test example

The glass transition temperature, transmittance, and haze were measured by the following method for resins prepared or prepared according to the above Examples and Comparative Examples, and the results are shown in Table 1 below. At this time, injection molded specimens could not be obtained with the copolymers according to Comparative Examples 1, 2, 3, and 5. On the other hand, in Fig. 1, in order to visually check the difference in transmittance and haze, photographs of specimens according to Example 4 and Comparative Examples 6 to 8 (Fig. 1(a) to Fig. 1(d), respectively) are shown.

(1) Glass transition temperature (Tg)

Using about 10 mg of a sample in a differential scanning calorimeter (Q200, TA Instrumnets), measured by heating at a heating rate of 10°C/min, and in accordance with ASTM D3418, a straight line extending from the low temperature side to the high temperature side, and glass The extrapolated glass transition initiation temperature Tg, which is the temperature at the intersection of the drawn broken lines, was obtained at the point where the gradient of the curve of the stepwise change portion of the transition became the maximum.

(2) Total light transmittance and haze

Using a 25-ton injection molding machine from Dongshin Hydraulic Co., it was injection-molded at a temperature of 230°C to 300°C with a width of 50 mm, a length of 70 mm, and a thickness of 3.0 mm to obtain a test piece. The total light transmittance and haze of the obtained specimen in accordance with ASTM D 1003 were measured using a measuring device of Nippon Denshoku's NDH-5000 model.

Referring to Table 1 and FIG. 1, when preparing a polyester carbonate copolymer by melt-condensation polymerization of a specific monomer mixture in a single process according to the present invention, polyarylate and polycarbonate are each polymerized and compounded using an extruder. Compared to the resulting resin, the haze is significantly reduced, and it can be seen that the transmittance is higher overall. However, when formulas 4 and 5 are composed of an aromatic compound, if the content is excessive (see Example 7), the transmittance and haze may be slightly lowered.

The glass transition temperature is similar to that of the polycarbonate/polyarylate (PC/PAR) alloy resin, and it can be seen that it can be sufficiently overcome by adjusting the monomer component. However, if the content of aromatic and aliphatic components is excessively skewed to either side, processing may be difficult due to high heat resistance or insufficient viscosity, so appropriate distribution should be made according to the use.

The preferred embodiments of the present invention have been described in detail above. The description of the present invention is for illustration only, and those of ordinary skill in the art to which the present invention pertains will be able to understand that other specific forms can be easily modified without changing the technical spirit or essential features of the present invention.

Therefore, the scope of the present invention is indicated by the claims to be described later rather than the detailed description, and all changes or modified forms derived from the meaning, scope, and equivalent concepts of the claims are included in the scope of the present invention. It must be interpreted.

Claims (10)

Polyester carbonate copolymer containing repeating units represented by the following formulas 6.1 to 6.4:
[Formula 6.1]

[Formula 6.2]

[Formula 6.3]

[Formula 6.4]

In Formulas 6.1 to 6.4, X1 is

, X2 is

, Y1 is

And Y2 is

to be. The method of claim 1,
The copolymer is a polyester carbonate copolymer, characterized in that the glass transition temperature (Tg) is 184 ~ 200 ℃. The method of claim 1,
The copolymer is a polyester carbonate copolymer, characterized in that the transmittance (ASTM D1003) is 89% or more. A method for producing a polyester carbonate copolymer comprising the step of melt-condensation polymerization of a monomer mixture comprising diphenyl carbonate, diphenyl terephthalate, bisphenol A, and bisphenol fullerene. delete delete delete The method of claim 4,
The melt condensation polymerization reaction is a first reaction step of 0.1 to 5 hours under a reduced pressure condition of 50 to 750 Torr, a temperature of 150 to 250 ℃; And a second reaction step that proceeds for 0.1 to 10 hours at a reduced pressure condition of 10 Torr or less and a temperature of 200 to 300° C., wherein the method for producing a polyester carbonate copolymer is performed. The method of claim 4,
The catalyst used in the melt condensation polymerization reaction, characterized in that it 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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