KR20130055219A

KR20130055219A - Blend of polylactic acid resin and copolyester resin having superior impact strength and heat resistance and articles using the same

Info

Publication number: KR20130055219A
Application number: KR1020110120864A
Authority: KR
Inventors: 박규태; 김종량; 신종욱; 강민구
Original assignee: 에스케이케미칼주식회사
Priority date: 2011-11-18
Filing date: 2011-11-18
Publication date: 2013-05-28
Also published as: KR101801705B1; TW201326300A; TWI561575B; WO2013073818A1

Abstract

Disclosed are a polylactic acid resin and a copolyester resin blend having excellent impact resistance and heat resistance, and molded articles using the same. The polylactic acid resin and the copolyester resin blend are polylactic acid resins; And a copolyester resin comprising a dicarboxylic acid component comprising a terephthalic acid residue and a diol component comprising 3 to 99 mol% cyclohexanedimethanol residues and 1 to 60 mol% isosorbide residues, The content of isosorbide moiety in the polylactic acid resin and the copolyester resin is 20 to 60% by weight based on the total blend.

Description

Blend of polylactic acid resin and copolyester resin having superior impact strength and heat resistance and articles using the same}

The present invention relates to a polylactic acid resin and a copolyester resin blend, and more particularly, to a polylactic acid resin and a copolyester resin blend having excellent impact resistance and heat resistance, and a molded article using the same.

Polylactic acid (PLA) resin is a plant-derived resin obtained from plants such as corn, and has biodegradable properties. Polystyrene resins, polyvinyl chloride (PVC) resins, and polyethylene (Polyethylene) Unlike petroleum-based resins such as), it is possible to reduce the environmental pollution, which is a disadvantage of petroleum-based plastic products, because it is effective in preventing the exhaustion of petroleum resources and suppressing carbon dioxide emissions. Accordingly, as the environmental pollution problem caused by waste plastics has emerged as a social problem, efforts are being made to expand the scope of application to general plastics (petroleum resins) such as food packaging materials, containers, and electronic product cases. However, polylactic acid resins are limited in application range compared to conventional petroleum resins because of their low impact resistance and heat resistance.

In order to solve this problem, a method of compensating for the disadvantages of the polylactic acid resin by selecting some of the existing petroleum-based plastic resin products and blending with the polylactic acid resin has been attempted. For example, Korean Patent Publication No. 10-2005-0056021 discloses a method of improving the low impact resistance of polylactic acid by blending polylactic acid and polycarbonate resin. In this case, however, as the content of the polycarbonate resin is increased in order to improve impact resistance and heat resistance, the specific gravity of the product of the petroleum-based plastic resin increases, and bisphenol-A (Bisphenol-A), which is a harmful substance due to the increase in the content of the polycarbonate resin, is increased. It is accompanied by the content of A). After all, there is a problem that results in a violation of the intended use of the polylactic acid resin.

Therefore, when blending with a polylactic acid resin, while maintaining the content of the bio-material to 20 to 60% by weight, while maintaining the environment-friendly, there is a need for a resin that can improve the heat resistance and impact resistance.

Accordingly, it is an object of the present invention to provide a polylactic acid resin and a copolyester resin blend having excellent heat resistance and impact resistance while maintaining environmental friendliness and molded products using the same.

In order to achieve the above object, the present invention, polylactic acid resin; And a copolyester resin comprising a dicarboxylic acid component comprising a terephthalic acid residue and a diol component comprising 3 to 99 mol% cyclohexanedimethanol residues and 1 to 60 mol% isosorbide residues, The content of the isosorbide moiety in the polylactic acid resin and the copolyester resin is 20 to 60% by weight relative to the total blend, to provide a polylactic acid resin and a copolyester resin blend.

The present invention also provides a molded product produced by molding the polylactic acid resin and the copolymerized polyester resin blend.

The polylactic acid resin and the copolyester resin blend according to the present invention are blended with a copolyester resin containing a polylactic acid resin and an isosorbide (bio monomer), thereby increasing the content of the copolyester resin, and thus the bio of the blend. It maintains a certain amount (20 to 60% by weight) of the material (polylactic acid resin and isosorbide), which is environmentally friendly, and has a high content of copolyester resin having high impact resistance and high heat resistance, thereby improving impact resistance and heat resistance of the blend. . In addition, unlike blending with other petroleum resins, it does not contain harmful substances such as bisphenol-A (Bisphenol-A), and can prevent bubbles during thermoforming, so a separate drying process is required when manufacturing molded products. It may not be additionally included, and may be molded at a relatively low processing temperature, thereby providing a time and economic advantage. In addition, the polylactic acid resin and the copolyester resin blend according to the present invention are materials of environmentally friendly molded products (sheets, packaging materials, containers, interior or exterior of electronic products, interior or exterior of automobiles, interior or exterior construction, etc.) It is useful as a material for beverages, food containers, medical containers and the like.

Hereinafter, the present invention will be described in detail.

The polylactic acid resin and the copolymerized polyester resin blend according to the present invention include a polylactic acid (PLA) resin and a copolymerized polyester resin in which isosorbide (biomonomer) is copolymerized as a diol component, The ratio of the material (isosorbide residue in the polylactic acid resin and the copolyester resin) is maintained at 20 to 60% by weight, which is environmentally friendly, and the notched Izod impact strength (ASTM D256 method, measuring temperature: 23 ° C) is 80 J / m. As described above, the heat deflection temperature (ASTM D648 method, pressure applied to the specimen: 0.455 MPa) is 80 ° C. or more, and is excellent in impact resistance and heat resistance.

As the polylactic acid resin used in the present invention, a conventional polylactic acid resin can be used without limitation, and a commercialized polylactic acid resin can be used. The polylactic acid resin is typically prepared from a monomer derived from L-lactic acid and / or D-lactic acid, and L- within a range that does not impair the effects of the present invention. It may also contain a certain amount of other monomers not derived from lactic acid or D-lactic acid. There are many methods for producing the polylactic acid resin, but the most representative method is the ring-opening polymerization of lactide (Lactide) prepared from lactic acid. However, the polycondensation reaction may be carried out directly without being limited thereto. Polylactic acid resins prepared from monomers derived from L- and D-lactic acids, respectively, are crystalline and have a high melting point. However, when prepared using L-lactide, D-lactide and meso-lactide derived from L-lactic acid, D-lactic acid, the content of L-lactide, D-lactide and meso-lactide Crystallinity and melting point can be freely adjusted according to the requirements, each component content can be adjusted according to the application.

The number average molecular weight of the polylactic acid resin is 10,000 to 500,000, preferably 30,000 to 300,000. When the number average molecular weight of the polylactic acid resin is less than 10,000, there is a fear that the mechanical properties such as impact resistance is not sufficiently expressed. When it exceeds 500,000, the production (polymerization) of the polylactic acid resin may be difficult, and excessive molecular weight Because of this, there is a fear that processing becomes difficult.

The copolyester resin used in the present invention is to improve the impact resistance and heat resistance of the polylactic acid resin and the copolyester resin blend, and to maintain the biomaterial content of the blend in a predetermined amount (60% by weight) or more, and is a terephthalic acid residue. The dicarboxylic acid component and a diol component comprising 3 to 99 mol% cyclohexane dimethanol residues, 1 to 60 mol% isosorbide (see formula 1) residues are copolymerized, the dika The acid moiety derived from the carboxylic acid component and the diol moiety derived from the diol component have repeating structures.

Here, the copolyester resin means a synthetic polymer prepared by a polycondensation reaction of at least one difunctional carboxylic acid with at least one difunctional hydroxyl compound. Typically the difunctional carboxylic acid is a dicarboxylic acid and the difunctional hydroxyl compound is a dihydric alcohol such as glycol or diol. In the present specification, the term "residue" means a certain part or unit which is included in the result of the chemical reaction when the specific compound participates in the chemical reaction and is derived from the specific compound. For example, each of "dicarboxylic acid residue" and "diol (glycol) residue" is derived from a diol component or part derived from a dicarboxylic acid component in a polyester formed by an esterification reaction or a polycondensation reaction. Means part. That is, when the dicarboxylic acid component and the diol (glycol) component are subjected to a conventional polyester polymerization reaction, it means a residue remaining after the hydrogen, hydroxy group or alkoxy group is removed. Accordingly, the dicarboxylic acid residue may be a dicarboxylic acid monomer or an acid halide or ester thereof (e.g., lower alkyl ester having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester). , Salts, anhydrides, or mixtures thereof. Thus, in the present specification, the terms "dicarboxylic acid", "terephthalic acid" and the like are useful for the polycondensation process with a diol for producing a high molecular weight polyester, dicarboxylic acid (terephthalic acid, etc.) and its dika And any derivatives of leric acid, such as acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof.

The dicarboxylic acid component of the copolyester resin contains 50 to 100 mol%, for example, 60 to 99.9 mol%, specifically 90 to 99.9 mol%, of the terephthalic acid moiety relative to the total dicarboxylic acid component. To improve the physical properties of the polyester resin, dicarboxylic acid residues such as aromatic dicarboxylic acid residues having 8 to 14 carbon atoms (excluding terephthalic acid residues), aliphatic dicarboxylic acid residues having 4 to 12 carbon atoms, and mixtures thereof It may contain 0 to 50 mol%, for example, 0.1 to 40 mol%, specifically 0.1 to 10 mol%. As an aromatic dicarboxylic acid which can form the said aromatic dicarboxylic acid residue, Naphthalene dicarboxylic acid, such as terephthalic acid, isophthalic acid, 2, 6- naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, etc. The aromatic dicarboxylic acid normally used for manufacture of a polyester resin can be illustrated, The aliphatic dicarboxylic acid which can form the said aliphatic dicarboxylic acid residue is 1, 4- cyclohexanedicarboxylic acid. Polyester resins such as cyclohexanedicarboxylic acid such as 1,3-cyclohexanedicarboxylic acid, phthalic acid, sebacic acid, succinic acid, isodecyl succinic acid, maleic acid, fumaric acid, adipic acid, glutaric acid, and azaraiic acid Illustrative linear, branched or cyclic aliphatic dicarboxylic acid components commonly used in the preparation of these compounds can be exemplified. Here, when the dicarboxylic acid residue (copolymerization monomer) other than the terephthalic acid residue is included, when the content of the dicarboxylic acid residue is too small or too large, the effect of improving the physical properties is insufficient, or rather, the polyester resin There is a fear that the physical properties of the.

The diol component of the copolyester resin is 3 to 99 mol%, preferably 3 to 99 mol%, based on the total diol component, a range corresponding to the following formula (1), more preferably 5 to 91 mol % Of cyclohexanedimethanol (1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, etc.) residues, 1 to 60 mol%, preferably 60 mol% Within the range not exceeding, the range corresponding to the following Equation 1, more preferably 4 to 40 mol% of isosorbide (In the following Equation 1, ISB mol% is the content of isosorbide residues, CHDM mol% is the content of cyclohexanedimethanol residues).

Equation 1 0.0012 (CHDM mol%) ² -0.2401 (CHDM mol%) + 11.136 ≤ ISB mol% ≤ -0.0122 (CHDM mol%) ² +0.0243 (CHDM mol%) +79.846

In addition, the diol component of the copolyester resin is 0 to 94 mol%, preferably 0.1 to 88 mol%, more preferably 0.1 to 80 mol% of 2 to 20 carbon atoms, preferably of 2 to 12 carbon atoms Diol residues such as aliphatic diol residues (except cyclohexanedimethanol residues and isosorbide residues). Diols capable of forming the aliphatic diol residues include ethylene glycol, diethylene glycol, triethylene glycol, propanediol (1,2-propanediol, 1,3-propanediol, etc.), 1,4-butanediol, and pentanediol. , Hexanediol (1,6-hexanediol, etc.), neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,2-cyclohexanediol, 1,4-cyclohexanediol, tetramethylcyclo Linear, branched or cyclic aliphatic diols, such as butanediol, preferably ethylene glycol.

If the content of the cyclohexanedimethanol residue in the diol component of the copolyester resin is less than 3 mol% with respect to the total diol components, the impact strength may be insufficient, and if it exceeds 99 mol%, isosorbide The residue content is less than 1 mol%, and there is a fear that the heat resistance is lowered. When the content of the isosorbide moiety is less than 1 mol% with respect to the total diol component, there is a fear that the heat resistance of the copolyester resin to be produced may be insufficient, and when it exceeds 60 mol%, the polyester resin may be yellowed. There is a fear. In addition, when the content of the diol residues (excluding cyclohexanedimethanol residues and isosorbide residues) exceeds 94 mol% with respect to the total diol components, there is a concern that the physical properties of the polyester resin may be lowered.

After preparing the specimen having a thickness of 3.2 mm using the copolymerized polyester resin, the notch Izod impact strength (ASTM D256 method, measuring temperature: 23 ° C.) is measured, and the impact strength of 50 J / m or more is preferable. Indicates. On the other hand, the notched Izod impact strength of the polyester resin copolymerized only with ethylene glycol and isosorbide usually shows a value of 50 J / m or less. When the co-polyester resin is annealed at 300 ° C. for 5 minutes, cooled to room temperature, and then scanned again at a temperature increase rate of 10 ° C./min (2nd Scan), the co-polyester resin is preferably 90 ° C. or more. It has a glass transition temperature (Tg). Further, after dissolving the co-polyester resin in orthochlorophenol (OCP) at a concentration of 1.2 g / dl, when the intrinsic viscosity was measured at 35 ℃, 0.35 dl / g or more, preferably 0.40 dl / g or more More preferably 0.45 dl / g or more. Since the copolyester resin is environmentally friendly, and excellent in heat resistance and impact resistance, blending with the polylactic acid resin may compensate for the low impact resistance and heat resistance of the polylactic acid resin.

The weight average molecular weight (Mw) of the copolyester resin is, for example, 10,000 to 200,000 (g / mol), preferably 20,000 to 100,000 (g / mol). When the weight average molecular weight of the copolyester resin is out of the above range, there is a fear that the workability of the blend is lowered or the physical properties of the blend are lowered.

The copolyester resin may be prepared by a conventional polyester production method, for example, esterifying the dicarboxylic acid and the diol compound (first step), and the esterification reaction product. It may be prepared through a poly-condensation reaction (second step). Specifically, the step of esterifying the dicarboxylic acid and diol compound, esterification of the dicarboxylic acid and diol compound at a pressure of 0 to 10.0 kg / ㎠ and 150 to 300 ℃ temperature for 1 to 24 hours Reaction or transesterification. The esterification conditions may be appropriately adjusted according to the specific properties of the polyester to be prepared, the molar ratio of the dicarboxylic acid component and glycol, process conditions, and the like. Specifically, preferred examples of the esterification conditions are 0 to 5.0 kg / cm 2, more preferably 0.1 to 3.0 kg / cm 2, 200 to 270 ° C., more preferably 240 to 260 ° C., 1 A reaction time of from 15 hours to more preferably 2 to 8 hours can be exemplified. The molar ratio of the dicarboxylic acid component and the diol component participating in the esterification reaction may be 1: 1.05 to 1: 3.0, for example, the content of cyclohexanedimethanol is 100 parts by weight of the dicarboxylic acid component. The total dicarboxylic acid component and the diol component can be added to 10 to 90 parts by weight, preferably 20 to 80 parts by weight. If the molar ratio of the diol component to the dicarboxylic acid component is less than 1.05, the unreacted dicarboxylic acid component may remain during the polymerization reaction and the transparency of the resin may be lowered. If the molar ratio exceeds 3.0, the polymerization reaction rate May be lowered or the productivity of the resin may be lowered. Catalysts may be selectively used to improve process time and yield of the esterification reaction, and the esterification reaction may be performed in a batch or continuous manner, and each raw material may be added separately, but diol It is preferable to add in the form of the slurry which mixed the dicarboxylic acid component with the component. In the case of the second polyester, a diol component such as isosorbide which is solid at room temperature can be dissolved in water or ethylene glycol, and then mixed with a dicarboxylic acid component such as terephthalic acid to form a slurry. In addition, water may be added to a slurry in which diol components such as dicarboxylic acid component, isosorbide and ethylene glycol are mixed to increase the solubility of isosorbide. It is also possible to use a slurry in which the beads are molten.

In addition, the poly-condensation reaction of the esterification product, the esterification reaction product of the dicarboxylic acid component and the diol component 1 at a temperature of 150 to 300 ℃ and a reduced pressure of 400 to 0.01 mmHg To react for 24 hours. This polycondensation reaction may be carried out at a reaction temperature of preferably 200 to 290 ° C, more preferably 260 to 280 ° C, and reduced pressure of preferably 100 to 0.05 mmHg, more preferably 10 to 0.1 mmHg. . When the reduced pressure condition of the polycondensation reaction is applied, glycol, which is a byproduct of the polycondensation reaction, may be removed. However, when the polycondensation reaction is out of the 400 to 0.01 mmHg reduced pressure range, there is a concern that the byproducts may be insufficient. In addition, when the polycondensation reaction occurs outside the temperature range of 150 to 300 ℃, there is a fear that the physical properties of the polyester resin produced. The polycondensation reaction can proceed for the required time until the intrinsic viscosity of the final reaction product reaches an appropriate level, for example for an average residence time of 1 to 24 hours. Preferably, the final attained vacuum degree of the polycondensation reaction is less than 2.0 mmHg, and the esterification reaction and the polycondensation reaction may be performed under an inert gas atmosphere.

In the preparation of the first and second polyesters, additives such as polycondensation catalysts, stabilizers, colorants, and the like may be used. Additives such as polycondensation catalysts or stabilizers may be added to the product of the esterification reaction or transesterification reaction before initiation of the polycondensation reaction, and mixed slurry comprising dicarboxylic acid and diol compound before the esterification reaction. Phase may be added, or may be added during the esterification step.

As the polycondensation catalyst, a titanium compound, a germanium compound, an antimony compound, an aluminum compound, a tin compound, or a mixture thereof can be used. Examples of the titanium compound include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate Nitrate, triethanolamine titanate, acetylacetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide / silicon dioxide copolymer, titanium dioxide / zirconium dioxide copolymer, and the like. Examples of the germanium compound include germanium dioxide (GeO ₂ ), germanium tetrachloride (germanium tetrachloride, GeCl ₄ ), germanium ethyleneglycoxide, germanium acetate, and germanium acetate using them. Coalescence, souls of these The compound etc. can be illustrated.

As the stabilizer, phosphorus compounds such as phosphoric acid, trimethyl phosphate, and triethyl phosphate may be used, and the amount thereof may be 10 to 100 ppm by weight based on the amount of phosphorus element based on the weight of the final polymer (copolymer polyester resin). . If the amount of the stabilizer added is less than 10 ppm, the stabilizing effect may be insufficient and the appearance of the final product may change to yellow. In addition, when the amount of the stabilizer is more than 100 ppm, it may not be possible to obtain a polymer having a desired high degree of polymerization.

The colorant is added to improve the color of the polymer, and may be used a conventional colorant such as cobalt acetate, cobalt propionate, and if necessary, an organic compound colorant may be used. It may be 0 to 100 ppm relative to the weight of the polymer (copolymer polyester resin).

The polylactic acid resin and the copolyester resin blend according to the present invention are, for example, 1 to 30 parts by weight, preferably 3 to about 100 parts by weight of the total polylactic acid resin and the copolyester resin blend. 20 parts by weight of other resin components (eg, polycarbonate, polyethylene, polypropylene, polymethylmethacrylate, etc.) and additive components may be further included.

Additives that may be included in the blend may include stabilizers having the ability to preserve the physical properties of the blend during processing, storage and use of the blend, such as oxidation stabilizers, thermal stabilizers, light stabilizers, UV stabilizers, and compatibilizers, Blends nucleating agents, chain-extenders, lubricants, impact modifiers, colorants, waxes, mold release agents, fragrances, foaming agents, plasticizers, hydrolysis inhibitors, unreacted and reactive substances It can be used for the purpose of processing, storage and use. In particular, glycidyl (Glycidyl-) group, maleic anhydride (Maleic anhydride-) group, epoxy (Epoxy-) group, isocyanate (Isocyanate-) group, amino (Amino-) group, carboxylic acid (Carboxyl Compatibilizers containing reactive functional groups, such as acid groups, oxazolin- (Oxazoline-) groups (e.g., ethylene-based reactive noses containing about 6-8% glycidyl reactor in the main chain) Copolymer or terpolymer reacts with the ends of the polylactic acid resin and the copolyester resin (Carboxyl acid (-COOH) and hydroxyl group (-OH)), respectively. In addition, the compatibility of the polylactic acid resin and the copolymerized polyester resin may be increased, and additional effects such as an impact reinforcing effect may be obtained according to the molecular structure or the structure of the main chain bonded to the reactive functional group. Non-limiting examples of the compatibilizer including the reactive group, Adipic Acid, Hexamethlylene diamine, Epoxy-based, p-Phenylene diisocyanate (PPDI), HDI (1,6-Hexamethylene diisocyanate) ), Toluene diisocyanate (TDI), 1,5-Naphthalene diisocyanate (NDI), Isoporon diisocyanate (IPDI), 4,4-Diphenylmethane diisocyanate (MDI), cyclohexylmethane diisocyanate (Ethylene-glycidyl methacrylate) Glycidylmetacrylate, Ethylene-Glycidylacrylate, Ethylene-Acrylic Ester-Glycidyl Acrylate Ethylene-Acrylic Ethylene-Glycidylacrylate Ester-Glycidyl Methacrylate), reactive polystyrene (Epocros) and the like may be exemplified, and the additives may be used depending on the use and purpose, but are not limited to those mentioned above.

The polylactic acid resin and the copolyester resin blend according to the present invention may be prepared by a conventional blending method, and may be molded by, for example, a molding method such as an injection, extrusion, compounding process, or the like. That is, it can be extruded or injected directly by simple blending, or cooled pelletized while blended and compounded by extrusion, and then crystallized, and can be used again for extrusion or injection using the obtained pellet-type blend chips.

In the polylactic acid resin and the copolyester resin blend according to the present invention, the content of isoide moiety (total biomaterial) in the polylactic acid resin and the copolyester resin is 20 to 60% by weight, preferably based on the total blend. Preferably 20 to 45% by weight, more preferably 21 to 38% by weight, most preferably 21 to 35% by weight. Accordingly, the content of the polylactic acid resin and the copolyester resin may be used within the range of the content of the entire biomaterial does not deviate from the range, for example, the content of the polylactic acid resin is 3 to 60 weight %, Preferably 4 to 40% by weight, more preferably 5 to 30% by weight, most preferably 6 to 20% by weight, the content of the copolyester resin is 40 to 97% by weight, preferably May be 60 to 96% by weight, more preferably 70 to 95% by weight, most preferably 80 to 94% by weight, and the additive may be added 1 to 30 parts by weight based on 100 parts by weight of the total blend. When the content of isoide moieties (total biomaterials) in the polylactic acid resin and the copolyester resin is less than 20% by weight, the effects of biodegradability, oil resource depletion, carbon gas emission suppression, etc., which are advantages of the polylactic acid resin May not be expressed, and if the content of the polylactic acid resin is more than 60% by weight, the heat resistance of the blend falls below the reference point may not be used in a specific molded product.

After the 3.0 mm thick specimen was prepared using the polylactic acid resin and the copolyester resin blend of the present invention, the notched Izod impact strength (ASTM D256 method, measurement temperature: 23 ° C) was measured. impact strength of at least / m, preferably at least 85 J / m, more preferably at least 90 J / m, most preferably at least 110 J / m.

In addition, after preparing a specimen size of 127 mm * 13 mm * 3 ~ 13 mm using the blend, the pressure applied to the specimen of the heat distortion temperature (Heat Distortion Temperature or Heat Deflection Temperature: HDT, ASTM D648 method is 0.455 The method of MPa) shows a heat deflection temperature of 80 ° C or higher, preferably 82 ° C or higher, more preferably 90 ° C or higher, and most preferably 100 ° C or higher. The blend exhibits excellent impact resistance and heat resistance (heat deformation temperature) is excellent in compatibility between the polylactic acid resin and the copolyester polyester resin, excellent impact resistance and heat resistance of the high content of the blended polyester resin is lowered in the blend It seems to have been reflected as it is.

The polylactic acid resin and the copolyester resin blend according to the present invention are molded through conventional molding processes such as injection, extrusion, extrusion blow, injection blow, and profile extrusion known in the art, and post-processing such as thermoforming processes using the same. It can be made into a molded article (Fiber, injection molding, sheet and film) of the appropriate shape as needed.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. The following examples are intended to illustrate the present invention, but the scope of the present invention is not limited by the following examples.

In addition, in the following Example and a comparative example, the performance evaluation method of a polymer (blend) is as follows.

(1) Heat Resistance (Heat Deformation Temperature (HDT)): After preparing a specimen size of 127 mm * 13 mm * 3 ~ 13 mm using the blend, heat distortion temperature (Heat Distortion Temperature or Heat Deflection Temperature: HDT, The pressure applied to the specimen in the ASTM D648 method is 0.455 MPa).

(2) Notched Izod Impact Strength: A 3.0 mm thick specimen was prepared using the blend, and notched in accordance with ASTM D256, and then measured at 23 ° C. using an Izod impact strength measuring instrument.

(3) Confirmation of Hazardous Substances: Check the presence and content of hazardous substances (Bisphenol-A, etc.) in the product using Nuclear Magnetic Resonance Analyzer (NMR).

Production Example 1 Preparation of Copolyester Resin

Based on 6 moles of terephthalic acid as the dicarboxylic acid component and 6 moles of terephthalic acid as the diol component, 138 g of 1,4-cyclohexanedimethanol, 313 g of ethylene glycol and 105 g of isosorbide were mixed in a 3L reactor equipped with a stirrer and an outlet condenser. The temperature was gradually raised to 255 ° C while esterifying. At this time, the generated water was discharged to the outside of the system, and when the generation and discharge of the water was completed, the reaction was transferred to the polycondensation reactor equipped with a stirrer, a cooling condenser, and a vacuum system. After adding the catalyst, stabilizer, and colorant to the esterification reaction at an appropriate ratio, the reactor was firstly depressurized to 50 mmHg at atmospheric pressure while increasing the internal temperature of the reactor from 240 ° C. to 275 ° C., and ethylene glycol was removed by low vacuum for 40 minutes. Then, the mixture was slowly depressurized to 0.1 mmHg and subjected to polycondensation reaction under high vacuum until the desired intrinsic viscosity was obtained, thereby preparing a copolymerized polyester resin. The weight average molecular weight (Mw) of the manufactured copolymerized polyester resin was 63,000 (g / mol), and the intrinsic viscosity was 0.76 (dl / g).

Production Example 2 Preparation of Copolyester Resin

Copolymerization was carried out in the same manner as in Preparation Example 1, except that 565 g of 1,4-cyclohexanedimethanol, 96 g of ethylene glycol and 789 g of isosorbide were used based on 6 moles of terephthalic acid and 6 moles of terephthalic acid as the diol component. Polyester resins were prepared. The weight average molecular weight (Mw) of the manufactured co-polyester resin was 37,000 (g / mol), and the intrinsic viscosity was 0.65 (dl / g).

Example 1 Preparation and Evaluation of Polylactic Acid Resin and Copolyester Resin Blend

3% by weight of polylactic acid resin chip having a number average molecular weight of 100,000 and 97% by weight of the copolymerized polyester resin chip prepared in Preparation Example 2 were placed in a twin screw extruder machine (TEM), and the cylinder temperature was 220 ° C and the die temperature. Blending at 210 ° C. and a screw speed of 200 rpm produced a polylactic acid resin and copolyester resin blend in pellet form. Using the above-described method, the heat deflection temperature, notched Izod impact strength and the presence of harmful substances were measured, and the results are shown in Table 1 below.

Example 2 Preparation and Evaluation of Polylactic Acid Resin and Copolymerized Polyester Resin Blend

Ethylene-based reaction type containing 17% by weight of polylactic acid resin chip having a number average molecular weight of 100,000, 75% by weight of copolymerized polyester resin chip prepared in Preparation Example 2, and about 8% of glycidyl reactor in the main chain Except that 8% by weight of terpolymer (Terpolymer), a polylactic acid resin and a copolyester resin blend of the pellet form was prepared in the same manner as in Example 1, and the thermal deformation temperature, notched Izod impact strength And the presence of hazardous substances was measured, and the results are shown in Table 1 below.

Example 3 Preparation and Evaluation of Polylactic Acid Resin and Copolymerized Polyester Resin Blend

25% by weight of polylactic acid resin chip having a number average molecular weight of 100,000, 65% by weight of the copolymerized polyester resin chip prepared in Preparation Example 2, and about 6% of glycidyl reactor in the main chain. Except that 10% by weight of polymer (Terpolymer) was used, the polylactic acid resin and the copolyester resin blend of pellets were prepared in the same manner as in Example 1, and the thermal deformation temperature, notched Izod impact strength and The presence of harmful substances was measured, and the results are shown in Table 1 below.

Example 4 Preparation and Evaluation of Polylactic Acid Resin and Copolymerized Polyester Resin Blend

35% by weight of polylactic acid resin chip having a number average molecular weight of 100,000, 52% by weight of the copolymerized polyester resin chip prepared in Preparation Example 1, and an ethylene-based reactive catalyst containing about 6% of glycidyl reactor in the main chain Except that 13% by weight of polymer (Terpolymer) was used, the polylactic acid resin and the copolyester resin blend of the pellet form was prepared in the same manner as in Example 1, the thermal deformation temperature, the notched Izod impact strength and The presence of harmful substances was measured, and the results are shown in Table 1 below.

Example 5 Preparation and Evaluation of Polylactic Acid Resin and Copolymerized Polyester Resin Blend

43% by weight of polylactic acid resin chip having a number average molecular weight of 100,000, 42% by weight of the copolymerized polyester resin chip prepared in Preparation Example 2, and an ethylene-based reactive catalyst containing about 8% of glycidyl reactor in the main chain Except that 15% by weight of polymer (Terpolymer) was used, the pellet was prepared in the same manner as in Example 1, polylactic acid resin and copolymer polyester resin blend, heat deformation temperature, notched Izod impact strength and The presence of harmful substances was measured, and the results are shown in Table 1 below.

Example 6 Preparation and Evaluation of Polylactic Acid Resin and Copolyester Resin Blend

55% by weight of polylactic acid resin chip having a number average molecular weight of 100,000, 30% by weight of copolymerized polyester resin chip prepared in Preparation Example 1, and an ethylene-based reactive type substrate containing about 8% of glycidyl reactor in the main chain. Except that 15% by weight of polymer (Terpolymer) was used, the pellet was prepared in the same manner as in Example 1, polylactic acid resin and copolymer polyester resin blend, heat deformation temperature, notched Izod impact strength and The presence of harmful substances was measured, and the results are shown in Table 1 below.

[Comparative Example 1] Preparation and evaluation of polylactic acid resin in pellet form

Except not using a copolyester resin, a polylactic acid resin in the form of pellets was prepared in the same manner as in Example 1, and the thermal deformation temperature, notched Izod impact strength and the presence of harmful substances were measured. The results are shown in Table 1 below.

Comparative Example 2 A polylactic acid resin and polycarbonate preparation and evaluation of the resin blend

30% by weight of polylactic acid resin chips having a number average molecular weight of 100,000 and 70% by weight of polycarbonate (PC) resin chips were placed in a Haake compounding facility, blended at a cylinder temperature of 260 ° C, a die temperature of 255 ° C, and a screw speed of 50 rpm. A polylactic acid resin and a polycarbonate resin blend in the form of pellets were prepared. Using the above-described method, the heat deflection temperature, notched Izod impact strength and the presence of harmful substances were measured, and the results are shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Izod impact strength
(J / m) 400 600 110 90 85 80 35 110 Heat distortion temperature
(℃ @ 455kPa) 110 105 100 90 82 80 55 100 Contains hazardous substances
Whether radish radish radish radish radish radish radish U Bio material
Content ratio (% by weight) 20.5 30.5 36.7 41.2 50.6 58.6 100 30

From Table 1, it can be seen that the polylactic acid resin and the copolyester resin blend according to the present invention have an excellent Notch Izod impact strength of 80 to 600 J / m and a heat deformation temperature of 80 to 110 ° C. In addition, harmful substances (such as bisphenol-A) are not leaked, and bio-materials (isolated residues of polylactic acid resin and copolyester resin) have a high content ratio (wt%) of 20 to 60 wt%, which is environmentally friendly. Can be.

Claims

Polylactic acid resins; And
A copolyester resin comprising a dicarboxylic acid component comprising a terephthalic acid residue and a diol component comprising 3 to 99 mol% cyclohexanedimethanol residues and 1 to 60 mol% isosorbide residues,
The content of the isosorbide moiety in the polylactic acid resin and the copolyester resin is 20 to 60% by weight based on the total blend, polylactic acid resin and copolyester resin blend.

The notched Izod impact strength (ASTM D256 method, measuring temperature: 23 ° C) of the blend of the polylactic acid resin and the copolyester resin is 80 J / m or more, and the heat deflection temperature (ASTM D648 method, specimen). The pressure applied: 0.455 MPa) is at least 80 ° C polylactic resin and copolyester resin blend.

The notched Izod impact strength of claim 1, wherein the content of isosorbide moiety in the polylactic acid resin and the copolyester resin is 20 to 45% by weight based on the total blend, and the notched Izod impact strength of the polylactic acid resin and the copolyester resin blend. (ASTM D256 method, measuring temperature: 23 ℃) is more than 85 J / m, heat deformation temperature (ASTM D648 method, pressure applied to the specimen: 0.455 MPa) is 82 ℃ or more, polylactic acid resin and copolyester Resin blends.

The notched Izod impact strength according to claim 1, wherein the content of isosorbide moiety in the polylactic acid resin and the copolyester resin is 21 to 38% by weight based on the total blend, (ASTM D256 method, measuring temperature: 23 ℃) is more than 90 J / m, the heat deformation temperature (ASTM D648 method, pressure applied to the specimen: 0.455 MPa) is more than 90 ℃, polylactic acid resin and copolyester Resin blends.

The notched Izod impact strength according to claim 1, wherein the content of isosorbide moiety in the polylactic acid resin and the copolyester resin is 21 to 35% by weight based on the total blend, (ASTM D256 method, measuring temperature: 23 ℃) is 110 J / m or more, heat deformation temperature (ASTM D648 method, pressure applied to the specimen: 0.455 MPa) is 100 ℃ or more, polylactic acid resin and copolymer polyester Resin blends.

The polylactic acid resin and copolyester resin blend of claim 1, wherein the polylactic acid resin has a number average molecular weight of 10,000 to 500,000.

The dicarboxylic acid component according to claim 1, wherein the dicarboxylic acid component is selected from the group consisting of 0 to 50 mol% of aromatic dicarboxylic acid residues having 8 to 14 carbon atoms, aliphatic dicarboxylic acid residues having 4 to 12 carbon atoms, and mixtures thereof. A polylactic resin and copolyester resin blend, further comprising a dicarboxylic acid residue selected.

The method of claim 1, wherein the cyclohexanedimethanol is selected from the group consisting of 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and mixtures thereof. , Polylactic acid resins and copolymerized polyester resin blends.

According to claim 1, wherein the content of isosorbide residues (ISB mol%) and the content of cyclohexane dimethanol residues (CHDM mol%) is in the range represented by the following formula 1, polylactic acid resin and copolymer poly Ester resin blends.
Equation 1 0.0012 (CHDM mol%) ² -0.2401 (CHDM mol%) + 11.136 ≤ ISB mol% ≤ -0.0122 (CHDM mol%) ² +0.0243 (CHDM mol%) +79.846

The polylactic resin and copolyester resin blend of claim 1, wherein the diol component comprises 8-91 mole percent cyclohexanedimethanol residues and 4-40 mole percent isosorbide residues.

The polylactic acid resin and copolymerization of claim 1, wherein the diol component further comprises an aliphatic diol residue having 2 to 20 carbon atoms (excluding cyclohexanedimethanol residue and isosorbide residue) having 0 to 94 mol%. Polyester resin blend.

The method of claim 11, wherein the aliphatic diol residue is ethylene glycol, diethylene glycol, triethylene glycol, propanediol, 1,4-butanediol, pentanediol, hexanediol, neopentyl glycol (2,2-dimethyl-1,3 -Propanediol), 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, tetramethylcyclobutanediol and mixtures thereof Polylactic acid resin and copolyester resin blend.

The polylactic acid resin and copolyester resin blend of claim 1, wherein the cyclohexanedimethanol residue is present in an amount of 10 to 90 parts by weight based on 100 parts by weight of the dicarboxylic acid component.

A molded article produced by molding the polylactic acid resin and the copolyester resin blend according to any one of claims 1 to 13.