KR102200887B1 - Impact modified eco-friendly polyester carbonate resin compositions and method for preparing same - Google Patents

Abstract

[화학식 2]

화학식 2에서, A는 치환 또는 비치환된 탄소수 6 내지 40의 아릴렌기, 또는 치환 또는 비치환된 탄소수 2 내지 40의 헤테로 아릴렌기이고, 구조내에 질소 산소, 인, 황, 규소, 할로겐 원소 또는 금속 원소가 포함될 수 있다.An eco-friendly polyester carbonate resin composition having high glass transition temperature and high transparency characteristics of conventional polycarbonate while improving impact strength, which is one of the major disadvantages of conventional bio-derived polycarbonate resin, is disclosed. The present invention provides a polyester carbonate resin composition comprising a polyester carbonate copolymer including a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and an acrylic impact modifier.
[Formula 1]

[Formula 2]

In Formula 2, A is a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 40 carbon atoms, and nitrogen oxygen, phosphorus, sulfur, silicon, halogen element or metal in the structure Elements may be included.

Description

Eco-friendly polyester carbonate resin composition with improved impact strength and its manufacturing method {IMPACT MODIFIED ECO-FRIENDLY POLYESTER CARBONATE RESIN COMPOSITIONS AND METHOD FOR PREPARING SAME}

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

In general, polymers such as polycarbonate and polyester are manufactured using raw materials derived from petroleum resources. However, in recent years, there is a concern about depletion of petroleum resources, and there is a demand for providing a polymer resin using raw materials obtained from biomass resources such as plants. In addition, since there is a concern that global warming due to an increase in carbon dioxide emission and accumulation causes climate change, etc., development of a polymer resin using plant-derived monomers having extremely low carbon emission during the manufacturing process is required.

Isosorbide (1,4:3,6-dianhydrohexitol, 1,4:3,6-dianhydrohexitol) is a plant resource such as corn and potatoes, unlike existing raw materials based on the petrochemical industry. It is a raw material obtained from When isosorbide is used as a monomer for engineering plastics such as polycarbonate, it has excellent thermal properties because it is structurally hard.

Conventionally, it has been proposed to use isosorbide as a plant-derived monomer to obtain a polycarbonate by esterification reaction with diphenyl carbonate (see Patent Document 1). Such isosorbide-polycarbonate has advantages such as high transparency, scratch resistance, and high heat resistance, but has a disadvantage in that its impact strength is significantly lower than that of commercially available polycarbonate due to the rigidity of the monomer structure itself. To solve this problem, there have been attempts to solve this by copolymerizing the diol part with 1,4-cyclohexanedimethanol (CHDM) having a flexible property in addition to isosorbide, but the heat resistance (Tg) is 150°C. It is lowered from the level to 90°C, and the impact strength is also significantly lower than that of the existing polycarbonate.

In addition, as a copolymerized polycarbonate of isosorbide and other dihydroxy compounds, a polycarbonate obtained by copolymerizing bisphenol A has been proposed (refer to Patent Document 2). By copolymerizing an isosorbide and a diol aliphatic compound, a homopoly of isosorbide Attempts have been made to improve the stiffness of carbonate (see Patent Document 3).

On the other hand, there is also a case of developing a plant-derived PET resin using terephthalic acid, isosorbide, 1,4-cyclohexanedimethanol, and ethylene glycol, which are raw materials for PET resin (see Patent Document 4). Due to the rigid structure of terephthalic acid and isosorbide, heat resistance can be increased, but the impact resistance is remarkably deteriorated, such as the molded article is easily damaged even by a small impact, and there is a problem in that an expensive catalyst must be used.

[Prior patent literature]

-Patent Document 1: British Patent Application Publication No. 1079686 (1967.08.16.)

-Patent document 2: Japanese Laid-Open Patent Publication No. 56-55425 (1981.05.16)

-Patent Document 3: Korean Patent Publication No. 10-1080669 (2011.11.01.)

-Patent Document 4: Korean Patent Application Publication No. 10-1558574 (2015.10.01.)

Accordingly, the present invention is an eco-friendly polyester carbonate resin composition having high glass transition temperature and high transparency characteristics of the existing polycarbonate while improving the impact strength, which is one of the major disadvantages of the conventional bio-derived polycarbonate resin. It is intended to provide a manufacturing method and a molded article manufactured using the method.

In order to solve the above problems, the present invention provides a polyester carbonate resin composition comprising a polyester carbonate copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and an acrylic impact modifier. do.

[Formula 1]

[Formula 2]

In Formula 2, A is a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 40 carbon atoms, and nitrogen oxygen, phosphorus, sulfur, silicon, halogen element or metal in the structure Elements may be included.

In order to solve the above another problem, the present invention is a polyester carbonate copolymer by condensation polymerization reaction of a monomer mixture including a compound represented by the following formula 3, a compound represented by the following formula 4, and a compound represented by the following formula 5 Manufacturing a; And it provides a method for producing a polyester carbonate resin composition comprising; and adding an acrylic impact modifier to the polyester carbonate copolymer.

[Formula 3]

[Formula 4]

[Formula 5]

In Formula 3 or 4, A is a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 40 carbon atoms, and nitrogen oxygen, phosphorus, sulfur, silicon, halogen elements in the structure Alternatively, a metal element may be included, and R is each independently hydrogen, an aliphatic having 1 to 6 carbon atoms, or an aromatic having 6 to 12 carbon atoms, and may include a cyclic form.

In addition, the compound represented by Formula 3 is diphenyl terephthalate, diphenyl isophthalate, diphenyl phthalate, diphenyl 4,4-biscyclohexane carboxylate, diphenyl succinate, diphenyl glutarate, diphenyl adipate , Selected from the group consisting of diphenyl pimelate, diphenyl suberate, diphenyl nonane-1,9-dicarboxylate, diphenyl biphenyl 4,4'-dicarboxylate and aliphatic diphenyl carboxylate compounds of a linear structure And the compound represented by Formula 4 is at least one selected from the group consisting of diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. It provides a method for producing a polyester carbonate resin composition characterized by.

In addition, the acrylic impact modifier is a rubber polymer in which at least one acrylic rubber monomer is polymerized, methyl methacrylate, styrene, alpha-methyl styrene, alkyl substituted styrene, acrylonitrile, methacrylonitrile, maleic anhydride, alkyl nuclear substituted It provides a method for producing a polyester carbonate resin composition, characterized in that at least one monomer selected from the group consisting of maleimide and phenyl substituted maleimide is graft-polymerized.

In addition, the acrylic impact modifier provides a method for producing a polyester carbonate resin composition, characterized in that it is added in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the polyester carbonate copolymer.

In addition, the resin composition is a specimen having a thickness of 3.0 mm and has a total light transmittance of 80% or more measured according to ASTM D 1003, an impact strength of 10 kg·cm/cm or more measured according to ASTM D 256, and a glass transition temperature (Tg). It provides a polyester carbonate resin composition, characterized in that 130 ~ 160 ℃.

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

According to the present invention, it is possible to provide an eco-friendly polyester carbonate resin composition that can effectively improve impact strength while maintaining excellent transparency and heat resistance by adding an acrylic impact modifier to a polyester carbonate copolymer prepared using a specific monomer. In addition, this makes it possible to provide materials to various fields such as sheets, containers, lenses, light diffusion, optics, and construction.

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.

The present inventors have repeatedly studied to develop an eco-friendly polyester carbonate resin having high glass transition temperature and high transparency characteristics of the existing polycarbonate while improving the impact strength, which is a disadvantage of the conventional bio-derived polycarbonate resin. , It was discovered that by adding an acrylic impact modifier to a polyester carbonate copolymer prepared using a specific monomer, it was possible to provide an eco-friendly polyester carbonate resin composition capable of effectively improving impact strength while retaining excellent transparency and heat resistance. This led to the present invention.

Accordingly, the present invention discloses a polyester carbonate resin composition comprising a polyester carbonate copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and an acrylic impact modifier.

[Formula 1]

[Formula 2]

In Formula 2, A is a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 40 carbon atoms, and nitrogen oxygen, phosphorus, sulfur, silicon, halogen element or metal in the structure Elements may be included.

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

The method for preparing a polyester carbonate resin composition according to the present invention is a polyester carbonate copolymer by condensation polymerization of a monomer mixture including a compound represented by the following formula 3, a compound represented by the following formula 4, and a compound represented by the following formula 5 Manufacturing a; And adding an acrylic impact modifier to the polyester carbonate copolymer.

[Formula 3]

[Formula 4]

[Formula 5]

In Formula 3 or 4, A is a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 40 carbon atoms, and nitrogen oxygen, phosphorus, sulfur, silicon, halogen elements in the structure Alternatively, a metal element may be included, and R is each independently hydrogen, an aliphatic having 1 to 6 carbon atoms, or an aromatic having 6 to 12 carbon atoms, and may include a cyclic form.

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

Here, the dicarboxyl compound represented by Formula 3 is, for example, diphenyl terephthalate, diphenyl isophthalate, diphenyl phthalate, diphenyl 4,4-biscyclohexane carboxylate, diphenyl succinate, diphenyl glutarate. , Diphenyl adipate, diphenyl pimelate, diphenyl suberate, diphenyl nonane-1,9-dicarboxylate, diphenyl biphenyl 4,4'-dicarboxylate and aliphatic diphenyl carboxylate compounds of linear structure It may be one or more selected from the group consisting of, preferably diphenyl terephthalate.

In addition, the carbonate diester compound represented by Formula 4 may be, 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. And, preferably, it may be diphenyl carbonate.

As a diol component used in the step of preparing the polyester carbonate copolymer, in the present invention, a compound represented by Chemical Formula 5, that is, isosorbide, is used as a main component, but depending on the application, 30 mol% or less of the total diol component, A diol component represented by the following formula (6) other than isosorbide may be used in an amount of preferably 20 mol% or less, more preferably 10 mol% or less.

[Formula 6]

In Formula 6, X may be an aliphatic having 2 to 40 carbon atoms or an aromatic having 6 to 40 carbon atoms, may include a cyclic form, and may be a heterogeneous compound containing nitrogen, oxygen, silicon, phosphorus or sulfur elements in the structure.

The compound represented by Formula 6 is, for example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptane Diol, 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'- Dichlorodiphenyl ether, 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) It may be one or more selected from the group consisting of fluorene, and preferably 1,4-cyclohexanedimethanol.

When the compound represented by Formula 6 is additionally used, the polyester carbonate copolymer includes a repeating unit represented by Formula 1 and a repeating unit represented by Formula 2, in addition to the repeating unit represented by Formula 7 and the following Formula 8 It may further include a repeating unit represented by.

[Formula 7]

[Formula 8]

In Formulas 7 and 8, X is an aliphatic having 2 to 40 carbon atoms or an aromatic having 6 to 40 carbon atoms, and may include a cyclic form, and may be a heterogeneous compound containing nitrogen, oxygen, silicon, phosphorus or sulfur elements in the structure. And A is a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 40 carbon atoms, and nitrogen oxygen, phosphorus, sulfur, silicon, halogen element or metal element in the structure Can be included.

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 condensation polymerization is a transesterification reaction of a multi-hydroxy group compound, a diester carbonate and a dicarboxylate compound. A multi-hydroxy group compound, a dicarboxylate compound, and a diester carbonate are mixed in the presence of an inert gas, and usually 120 It is reacted at ~260°C. The degree of decompression is changed step by step, and finally, the resulting phenols are removed from the reaction system to 133 Pa or less. The reaction time is usually about 1 to 5 hours.

The polyester carbonate copolymer prepared through the above reaction includes, for example, a repeating unit represented by the following formula (9).

[Formula 9]

In Formula 9, x is 0 ≤ ≤ x ≤ ≤ 1, y is 0 <y <1, and X is a diol monomer excluding isosorbide. Here, if the amount of Chemical Formula 3 is x, the amount of Chemical Formula 4 is determined as 1-x, and if the amount of Chemical Formula 5 is y, the amount of Chemical Formula 6 is determined as 1-y. In addition, X and A in Chemical Formula 9 are as described above.

In the process of synthesizing the polyester carbonate according to the present invention, a polymerization catalyst may be used to speed up the polymerization rate. Examples of the polymerization catalyst include alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, hydroxides of alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and strontium hydroxide, hydroxides of boron or aluminum, alkali metal salts, alkaline earth metal salts, and quaternary ammonium salts. , Alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal organic acid salt, zinc compound, boron compound, silicon compound, germanium compound, organic tin compound, lead compound, antimony compound, manganese compound, titanium compound, zirconium compound, etc. A catalyst usually used for an esterification reaction or a transesterification reaction is 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 ^-9 to 1×10 ^-5 equivalents, more preferably 1×10 ^-8 to 5×10 ^-6 equivalents, per 1 mole of dihydric phenol of the raw material. Choose from a range.

In addition, in the condensation polymerization reaction, in order to reduce the phenolic end group, at the end or after the polycondensation reaction, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenylcarbonate, 2-ethoxy Compounds such as carbonylphenylphenyl carbonate can be added.

In the transesterification method, it is preferable to use a deactivator that neutralizes the activity of the catalyst. The amount of such deactivator is preferably used in a ratio of 0.5 to 50 moles based on 1 mole of the remaining catalyst. In addition, it is used in a ratio of preferably 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, and particularly preferably 0.01 to 100 ppm with respect to the aromatic polycarbonate after polymerization. As the deactivating agent, a phosphonium salt such as tetrabutylphosphonium salt of dodecylbenzenesulfonate, an ammonium salt such as tetraethylammonium dodecylbenzyl sulfate, and the like are preferably mentioned.

In the present invention, the step of adding an acrylic impact modifier is performed after preparing the polyester carbonate copolymer.

The acrylic impact modifier added in the present invention is specific only for the specific composition, that is, a polyester carbonate copolymer composed of a monomer including a compound represented by Formula 3, a compound represented by Formula 4, and a compound represented by Formula 5. As an impact modifier that realizes the effect, it provides excellent impact strength without deteriorating transparency and heat resistance.

Although it is not specifically limited to such an acrylic impact modifier, methyl methacrylate, styrene, alpha-methyl styrene, alkyl substituted styrene, acrylonitrile, methacrylonitrile, anhydrous in the rubber polymer in which at least one acrylic rubber monomer is polymerized. One or more monomers selected from the group consisting of maleic acid, alkyl nuclear substituted maleimide, and phenyl nuclear substituted maleimide may be preferably used for graft polymerization, and styrene-methylmethacrylate-butylacrylate copolymer (styrene- methyl methacrylate-butylacrylate copolymer) or polymethyl methacrylate-co-butyl methacrylate may be more preferably used, and styrene-methyl methacrylate-butyl acrylate copolymer (styrene- methyl methacrylate-butylacrylate copolymer) can be used most preferably. At this time, the content of rubber in the impact modifier is preferably 20 to 80% by weight.

The impact modifier may be added in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the polyester carbonate copolymer, preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, even more preferably May be added in an amount of 8 to 12 parts by weight. Within the above content range, the impact strength reinforcing effect is excellent without deteriorating transparency and heat resistance.

In the present invention, an additive suitable for the intended use or effect may be further included. For example, by adding an ultraviolet absorber, a hindered amine light stabilizer, a release agent, an epoxy compound, a heat stabilizer, an antioxidant, etc., it can be applied for various purposes.

In one embodiment, the polyester carbonate resin composition may further include an ultraviolet absorber.

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 copolymer. 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, as an embodiment, the polyester carbonate resin composition may further include a hindered amine light stabilizer.

As the hindered amine light stabilizer, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis-(1,2,2,6,6-pentamethyl-4-p) Peridyl) sebacate, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6 -Tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]], N,N'-bis(3-aminopropyl ) Ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidylamino)-6-chloro-1,3,5-triazine Condensate, dibutylamine-1,3,5-triazine-N,N'-bis(2,2,6,6)-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N -(2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate or a mixture of two or more thereof.

The hindered amine light stabilizer may be used in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the polyester carbonate copolymer. As the hindered amine light stabilizer is used in the above range, bleeding of the hindered amine light stabilizer to the surface of the polyester carbonate resin composition and mechanical properties of various molded articles are not deteriorated, and the polyester carbonate resin composition of the present invention The weather resistance of a molded article formed by molding can be improved.

In addition, in one embodiment, the polyester carbonate resin composition 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 copolymer.

In addition, in one embodiment, the polyester carbonate resin composition 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 copolymer. 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, in one embodiment, the polyester carbonate resin composition 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 copolymer.

On the other hand, in one embodiment, the polyester carbonate resin composition 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 copolymer.

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, in one embodiment, the polyester carbonate resin composition 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. Therefore, by adding the acrylic impact modifier to the polyester carbonate copolymer, which is a base resin, it has a higher impact strength without changing the existing equipment, and a biopolyester carbonate resin composition having high transparency and high heat resistance by solving the existing mixing problem. Can be manufactured.

A more preferable aspect of the twin screw extruder is as follows. As for the screw shape, one, two and three thread screw screws can be used. Further, as the extruder, a vent capable of degassing moisture in the raw material or volatile gas generated from the melt-kneaded resin can be preferably used. In addition, it is also possible to install a screen in the zone in front of the die section of the extruder to remove foreign substances and the like mixed in the raw material for extrusion, and remove foreign substances from the resin composition. Examples of the screen include a wire mesh, a screen changer, and a sintered metal plate (such as a disk filter).

The polyester carbonate resin composition prepared as described above improves the impact strength, which is a disadvantage of the existing bio-derived polycarbonate resin, while realizing the characteristics of high glass transition temperature and high transparency of polycarbonate. The corresponding resin composition is a specimen having a thickness of 3.0 mm and has a total light transmittance of 80% or more measured according to ASTM D 1003, an impact strength of 10 kg·cm/cm or more, measured according to ASTM D 256, and a glass transition temperature (Tg). It may be 130 to 160, preferably the total light transmittance is 85% or more, the impact strength is 25kg·cm/cm or more, and the glass transition temperature (Tg) may be 145 to 160.

After the resin composition is manufactured in the form of pellets, it may 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.

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 abbreviations of the compounds used in the description of Examples are as follows.

-ISS: isosorbide

-DPC: diphenyl carbonate

-DPT: diphenyl terephthalate

-CHDM: 1,4-cyclohexanedimethanol

-Acrylic impact modifier (styrene-methyl methacrylate-butylacrylate copolymer): IR-441 (manufactured by MRC)

-Butadiene-based impact modifier: EM-500 (product of LG Chemical)

-Silicone impact modifier: S-2001 (made by Metablene)

Example 1

After cleaning the reaction vessel without foreign matter, nitrogen purging was performed to remove oxygen in the reaction vessel as much as possible. For 100 parts by weight of ISS, 131 parts by weight of DPC, 22 parts by weight of DPT, and 2 ppm of potassium hydroxide as a catalyst (based on ISS) were added to a 1L glass reaction vessel, and the temperature of the reaction tank was set to 150 to dissolve and uniformly stir the input material in a nitrogen atmosphere. After heating to, the stirrer was rotated at 100 rpm when the stirrer rotated smoothly when turned by hand. Subsequently, while the pressure was reduced from normal pressure to 200 Torr and the reaction tank temperature was reduced to 180 over 1 hour and heated, the generated phenol was removed from the inside of the reactor. Then, while maintaining the reaction vessel at 190 for 30 minutes, the pressure was reduced to 100 Torr and the temperature of the reaction vessel was increased to 210 over 30 minutes over 30 minutes, and the generated phenol was discharged from the reaction vessel to remove. Subsequently, as the torque of the stirrer increased and the viscosity increased, the pressure was finally increased to 0.1 Torr and the temperature was increased to 260 to remove additional phenol. After reaching a predetermined stirring torque, the reaction was terminated and the resulting melt was pelletized to prepare a base resin. Subsequently, an acrylic impact modifier was added to the base resin in an amount of 10 parts by weight to 100 parts by weight of the base, and extruded with a twin screw extruder at 230 to 290°C to prepare a final resin composition in the form of a pellet.

Example 2

A resin composition was prepared in the same manner as in Example 1, except that the acrylic impact modifier was added in an amount of 5 parts by weight in Example 1.

Example 3

A resin composition was prepared in the same manner as in Example 1, except that the acrylic impact modifier was added in an amount of 20 parts by weight in Example 1.

Example 4

A resin composition was prepared in the same manner as in Example 1, except that the acrylic impact modifier was added in an amount of 30 parts by weight in Example 1.

Example 5

A resin composition was prepared in the same manner as in Example 1, except that the acrylic impact modifier was added in an amount of 40 parts by weight in Example 1.

Comparative Example 1

A resin composition was prepared in the same manner as in Example 1, except that the impact modifier was not added in Example 1.

Comparative Example 2

A resin composition was prepared in the same manner as in Example 1, except that a butadiene-based impact modifier was added instead of the acrylic impact modifier in Example 1.

Comparative Example 3

A resin composition was prepared in the same manner as in Example 1, except that a silicone-based impact modifier was added instead of the acrylic impact modifier in Example 1.

Comparative Example 4

In Example 1, a resin composition was prepared in the same manner as in Example 1, except that the content was adjusted to 150 parts by weight of DPC, 20 parts by weight of CHDM, and 10 parts by weight of an acrylic impact modifier for 100 parts by weight of ISS.

Test example

For the resin compositions prepared according to the above Examples and Comparative Examples, transparency, impact strength, and heat resistance were measured by the following method, and the results are shown in Table 1 below. At this time, the injection molded specimen could not be obtained with the copolymer according to Comparative Example 9.

(1) Transparency (total light transmittance, %)

The prepared resin composition was injection-molded to a width of 50 mm, a length of 70 mm, and a thickness of 3.0 mm at a temperature of 190 to 250 using an injection molding machine to prepare a specimen. Thereafter, using a measuring device of Nippon Denshoku's NDH-5000 model, the total light transmittance of the obtained specimen was measured according to ASTM D 1003.

(2) Impact strength (kgcm/cm)

After drying the prepared resin composition at 120° C. for 3 hours or more, the specimen was injected using an injection machine. Then, Izod impact strength was measured using ASTM D 256 standards.

(3) Glass transition temperature (Tg, °C)

Using about 10 mg of a sample in a differential scanning calorimeter (Q200, TA Instrumnets), measured by heating at a heating rate of 10/min, and in accordance with ASTM D 3418, a straight line extending from the low temperature side to the high temperature side, and the glass transition The extrapolated glass transition start 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 stepped change portion of is maximum.

Referring to Table 1, according to the present invention, a dihydroxy compound containing isosorbide is used as a raw material, but a specific dicarboxyl compound is used in combination with a diester carbonate monomer and a specific impact modifier is added to prepare it through a condensation polymerization reaction. In this case, it can be confirmed that an eco-friendly polyester carbonate resin composition having excellent impact strength can be obtained while maintaining excellent transparency and heat resistance without changing the existing process. The impact strength showed high impact strength when the acrylic impact modifier was added in an amount of 10 to 20 parts by weight based on 100 parts by weight of the base resin, and showed the best result at the level of 10 parts by weight.

On the other hand, when the acrylic impact modifier is not added (Comparative Example 1), the impact strength is significantly reduced, and when using the acrylic impact modifier and other types of impact modifiers (Comparative Examples 2 and 3), the transmittance and impact strength are significantly lowered. have.

On the other hand, even if an acrylic impact modifier is used, the composition of the base resin is different from the composition according to the present invention, and when applied to an existing bio-derived polycarbonate (Comparative Example 4), since the heat resistance is significantly lowered, the acrylic impact modifier is It can be seen that specific effects are implemented only for the polyester carbonate copolymer of a specific composition according to the present invention.

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 (7)

A polyester carbonate resin composition comprising a polyester carbonate copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and an acrylic impact modifier:
[Formula 1]

[Formula 2]

In Formula 2, A is a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 40 carbon atoms, and nitrogen oxygen, phosphorus, sulfur, silicon, halogen element or metal in the structure Elements may be included. Preparing a polyester carbonate copolymer by performing a condensation polymerization reaction of a monomer mixture including a compound represented by the following Formula 3, a compound represented by the following Formula 4, and a compound represented by the following Formula 5; And
Adding an acrylic impact modifier to the polyester carbonate copolymer;
Polyester carbonate resin composition manufacturing method comprising:
[Formula 3]

[Formula 4]

[Formula 5]

In Formula 3 or 4, A is a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 40 carbon atoms, and nitrogen oxygen, phosphorus, sulfur, silicon, halogen elements in the structure Alternatively, a metal element may be included, and R is each independently hydrogen, an aliphatic having 1 to 6 carbon atoms, or an aromatic having 6 to 12 carbon atoms, and may include a cyclic form. The method of claim 2,
The compound represented by Formula 3 is diphenyl terephthalate (1,4-Benzenedicarboxylic acid, diphenyl ester), diphenyl isophthalate (1,3-Benzenedicarboxylic acid, diphenyl ester), and diphenyl phthalate (1,2-Benzenedicarboxylic acid). , diphenyl ester) is at least one selected from the group consisting of,
The compound represented by Formula 4 is a polyester carbonate, characterized in that at least one selected from the group consisting of diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate and dibutyl carbonate Resin composition manufacturing method. The method of claim 2,
The acrylic impact modifier is a rubber polymer in which at least one acrylic rubber monomer is polymerized, methyl methacrylate, styrene, alpha-methyl styrene, alkyl substituted styrene, acrylonitrile, methacrylonitrile, maleic anhydride, alkyl nuclear substituted male A method for producing a polyester carbonate resin composition, characterized in that at least one monomer selected from the group consisting of mid and phenyl substituted maleimide is graft-polymerized. The method of claim 2,
The acrylic impact modifier method for producing a polyester carbonate resin composition, characterized in that added in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the polyester carbonate copolymer. The method of claim 1,
The resin composition is a specimen having a thickness of 3.0 mm and has a total light transmittance of 80% or more measured according to ASTM D 1003, an impact strength of 10 kg·cm/cm or more, measured according to ASTM D 256, and a glass transition temperature (Tg). Polyester carbonate resin composition, characterized in that 130 ~ 160 ℃. A molded article comprising the polyester carbonate resin composition according to claim 1.