Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
  • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/672—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/02—2 layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
  • B32B2250/244—All polymers belonging to those covered by group B32B27/36
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
  • B32B2307/21—Anti-static
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/306—Resistant to heat
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/308—Heat stability
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/402—Coloured
  • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/558—Impact strength, toughness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/738—Thermoformability
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2439/00—Containers; Receptacles
  • B32B2439/70—Food packaging
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

• the present invention relates to a multilayer polyester sheet and molded articles thereof. More specifically, the present invention relates to a multilayer polyester sheet and molded articles thereof having high physical properties such as high heat resistance, chemical resistance and impact resistance, and having excellent appearance characteristics, wherein the multilayer polyester sheet and molded articles thereof include food, It can be used for packaging cases or thermoformed products of various products.
• a multilayer sheet including two or more polymer resin sheets is used, and in particular, a multilayer sheet including a polyester resin sheet having low physical cost and suitable properties for packaging sheets is widely used.
• multilayer polyester sheets containing polyester resins which have been previously known, do not sufficiently secure heat resistance, chemical resistance and layer resistance above an appropriate level, and are deformed by a heat source or a chemical, or have a shape or structure due to external lamination or pressure. There was a limit to deformation.
• the present invention exhibits physical properties such as high heat resistance and chemical resistance and impact resistance. It is to provide a multilayer polyester sheet having excellent appearance properties. Moreover, this invention is providing the molded article containing the said multilayer polyester sheet.
• a base layer including a thermoplastic resin; And a coating layer formed on at least one side of the base layer and containing a polyester resin comprising a moiety of 51 to 85 mole% of isosorbide and a residue of a dicarboxylic acid component and a residue of a dicarboxylic acid component.
• a multilayer polyester sheet comprising.
• a molded article produced using the multilayer polyester sheet is also provided.
• 'residue' means a certain part or unit included in the result of the chemical reaction and derived from the specific compound when the specific compound participates in the chemical reaction.
• each of the 'residue' of the dicarboxylic acid component or the 'residue' of the diol component may be a part or diol component derived from a dicarboxylic acid component in a polyester formed by an esterification reaction or a polycondensation reaction. It means the part that originated.
• the substrate layer comprising a thermoplastic resin; And a coating layer formed on at least one side of the base layer and containing a polyester resin comprising a moiety of 51 to 85 mole% of isosorbide and a residue of a dicarboxylic acid component and a residue of a dicarboxylic acid component.
• the multi-ply polyester sheet containing may be provided.
• the present inventors have conducted research on the synthesis of a multilayer polyester sheet having more improved physical properties, and have 1, 4-cyclodimethane with 51 mol% to 85 mol%, preferably 52 mol% to 70 mol%.
• the polyester resin prepared using the diol component containing isosorbide of is applied to the coating layer, it exhibits excellent physical properties such as high heat resistance, chemical resistance and impact resistance.
• a multilayer polyester sheet having can be provided and completed the invention.
• the coating layer may have a high heat resistance and chemical resistance by containing a diol containing 51 mol% to 85 mol% of isosorbide, a polyester resin containing a residue of a component and a residue of a dicarboxylic acid component, and the like.
• the content of isosorbide in the diol component of the polyester resin contained in the coating layer is less than 51 mol%, the glass transition temperature of the polyester resin contained in the coating layer is lowered, or Oven test B type of the multilayer polyester sheet In such a case that the deformation temperature is lower than 80 ° C., the heat resistance of the multilayer polyester sheet may not be sufficiently secured.
• the content of isosorbide in the diol component of the pulley ester resin contained in the coating layer is less than 51 mol%, the multilayer polyester sheet of the above embodiment may be easily deformed or modified by an organic solvent or an organic compound.
• the multilayer polyester sheet of the embodiment is a layer or low temperature resistant You may not be able to secure enough.
• polyester contained in the coating layer If the content of isosorbide in the diol component of the resin is more than 85 mol%, the molecular structure of the polyester resin contained in the coating layer may not be densely formed, and the polyester resin, coating layer, or the above-described embodiment may be contained in the coating layer.
• Mechanical properties of the multilayer polyester sheet of the example for example, the layer resistance, wear resistance and the like can be lowered.
• the thermoplastic resin included in the base layer may include a polyester resin.
• the polyester resin are not particularly limited, for example, polyethylene polycondensed terephthalic acid and ethylene glycol Terephthalate, PET-based copolymerized polyester resins in which a part of terephthalic acid is changed to another dicarboxylic acid, or a part of ethylene glycol is added to another diol or the like can be used.
• Other diols used in the synthesis of the base layer thermoplastic resin may include neopentyl glycol, 1,4-cyclonucleodimethanol, propylene glycol, tetramethylene glycol, and the like.
• the substrate layer may further include a recycled resin together with the thermoplastic resin.
• the recycled resin may be obtained by recycling a molded article manufactured using the multilayer polyester sheet or the multilayer polyester sheet.
• a method of crushing or pulverizing and drying the molded article manufactured using the multilayer polyester sheet or the multilayer polyester sheet may be used.
• the multilayer polyester sheet or the molded article manufactured using the multilayer polyester sheet is crushed or pulverized, and impurities are removed while hot air drying or dehumidifying drying at 60 ° C. to locrc, and then the pulverized product is mixed with other resins and melted. Extrusion and copolymerization may be used.
• the base layer comprises recycled resin in an amount of 1% by weight to 70% by weight, or 10% by weight to 60% by weight, or 30% by weight to 50% by weight of the total polyester resin included in the substrate layer. can do.
• the deformation temperature by the Oven test B type may be increased by at least 1 ° C., such that the heat resistance of the multilayer polyester sheet may be improved. .
• the above-described degree of heat resistance improvement may not be very high.
• the content of the recycled resin contained in the base layer is more than 70% by weight, as the content of other components or impurities contained in the recycled resin is increased, the appearance characteristics such as transparency or color of the base layer is The physical properties and appearance characteristics of the multilayer polyester sheet may also be lowered accordingly.
• the intrinsic viscosity of the thermoplastic resin included in the base layer is not particularly limited, but is preferably in the range of 0.40 ⁇ / g to 1.20 dl / g.
• the intrinsic viscosity of the thermoplastic resin included in the substrate layer is less than 0.40 ⁇ / g, poor appearance may occur with respect to flow during extrusion.
• the intrinsic viscosity of the thermoplastic resin included in the substrate layer is more than 1.20 ⁇ / g, the pressure of the extruder may increase due to the increase in the viscosity of the melt in the manufacture of the multilayer polyester sheet may not be smooth film forming process, the pressure rise When the temperature of the extruder is raised to solve the problem, physical properties may decrease due to deformation due to heat.
• the thermoplastic resin included in the base layer may have a weight average molecular weight of 5, 000 to 500, 000, preferably 10, 000 to 350, 000.
• the weight average molecular weight of the thermoplastic resin included in the base layer is less than 5,000, mechanical properties of the thermoplastic resin, for example, impact resistance, wear resistance, and the like may decrease.
• the weight average molecular weight of the thermoplastic resin included in the base layer is more than 500, 000, as the melting point of the thermoplastic resin is increased, not only the workability may be lowered, but also the viscosity is increased, so that the extruder The pressure may rise and the film forming process may not be smooth.
• thermoplastic resin contained in the said base material layer there is no restriction
• the dicarboxylic acid component used in the synthesis of the polyester resin contained in the coating layer may include an aromatic dicarboxylic acid component, preferably terephthalic acid.
• the dicarboxylic acid component may be a dicarboxylic acid such as terephthalic acid, an alkyl ester thereof (lower alkyl ester having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester) and / or an acid anhydride thereof (acid anhydride) may be used to react with a diol component to form a dicarboxylic acid moiety such as terephthaloyl moiety.
• the dicarboxylic acid component used in the synthesis of the polyester resin contained in the coating layer contains terephthalic acid
• the heat resistance, chemical resistance or weather resistance of the polyester resin contained in the coating layer for example, by UV Physical properties such as molecular weight reduction or prevention of yellowing
• the diol component used in the synthesis of the polyester resin contained in the coating layer may include 51 mol% to 85 mol% of isosorbide, and a residual aliphatic diol component.
• the production method for synthesizing the polyester resin contained in the coating layer according to the content of the isosorbide is not particularly limited, for example, to prepare a polyester resin containing isosorbide to satisfy the content, or to vary the content It can be prepared through the mixing between the various polyester resin containing isosorbide.
• the diol component used in the synthesis of the polyester resin contained in the coating layer may further include a residual amount of aliphatic digal component in addition to the isosorbide.
• the 'aliphatic diol component' means a diol component except the isosorbide, and may include an aliphatic diol compound having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms.
• aliphatic dialkyl compounds examples include 4- (hydroxymethyl) cyclonucleic acid carboxylic acid, 4,4- (oxybis (methylene) bis) cyclonucleic acid methanol, diethylene glycol, ethylene glycol, propanediol (1,2 -Propanediol, 1,3 'propanediol, etc.), 1, 4-butanedi, 2, 2-dimethyl- 1, 3-propanediol, 1,6' dinucleic acid diol, 1, 2-cyclonucleodioxide, 1, Linear, branched or cyclic aliphatic diol components such as 2-cyclonucleodimethanol, 1,3′cyclonucleodimethane, 1,4-cyclonucleic acid dimethanol, and the like, but specific examples of aliphatic diethyl compounds are limited thereto. It doesn't happen.
• the polyester resin contained in the coating layer may have a glass transition degree of 1201: to 165 ' t.
• the glass transition degree of the polyester resin contained in the coating layer can be confirmed through DSC measurement data, etc.
• the polyester resin contained in the coating layer is kept at 300 ° C. for 5 minutes and gradually cooled to room temperature. After that, the method of rescanning at a temperature rising rate of 10 ° C An in may be used. If the glass jeonyieun view of the polyester resin contained in the coating layer is less than 120 ° C, and the contents can be filled, or that the multi-layer, a polyester sheet deformed by the external heat source generated in the course of transportation. On the other hand, the glass transition contained in the coating layer is 165 ° C. If exceeded, a large amount of ' thermal energy may be required in the processing for forming the multilayer polyester sheet.
• the multilayer polyester sheet may have a deformation temperature of more than 90 ° C by Oven test B type.
• the Oven test B type is a method of measuring a deformation temperature at which the deformation starts in appearance by gradually increasing the temperature by putting a sample of a predetermined standard prepared using the multilayer polyester sheet into an oven.
• the deformation temperature by the Oven test B type is less than 90 ° C, ' the multilayer polyester sheet may be deformed by the heat generated in the process of layering or transporting the contents.
• the multilayer polyester sheet is the base layer and the coating layer, respectively
• the coating layer may be formed on at least one surface of the substrate layer, and the multilayer polyester sheet may include one or more substrate layers.
• the multilayer polyester sheet may include one base layer and a coating layer formed on one or both sides of the base layer, and is also located between two or more base layers and a neighboring base layer of the base layers. It may include the coating layer.
• the multilayer polyester sheet may have a thickness ratio of the coating layer to the base layer thickness of 5 % to 75%, or 10% to 50%, or 20% to 30%.
• the entire thickness of the multilayer polyester sheet is 30 kPa to 5500, and the thickness of the coating layer may be changed at a ratio of 1% to 50% of the thickness of the multilayer polyester sheet.
• the thickness ratio of the coating layer can be calculated as the ratio of the thickness of the total of these double-side coating layer when there is a covering insect on both sides of the substrate layer.
• the thickness ratio of the coating layer to the substrate layer thickness may be calculated based on the sum of all the substrate layer thicknesses and the sum of all the coating layer thicknesses.
• the thickness of the base layer and the coating layer may be determined according to the properties or applications of the multilayer polyester sheet, for example, the base layer is 20 m to 3000 thickness, the coating layer is 10 m to 2500 / an thickness Can have have.
• the thickness of each coating layer may be the same or different, and the thickness of the coating layer per layer is preferably 10 Pa to 500.
• the intrinsic viscosity of the polyester resin contained in the coating layer may be 0.40 dC / g to 0.60 M / g. If the intrinsic viscosity of the polyester resin contained in the coating layer is less than 0.40 ⁇ / g, poor appearance may occur with respect to the flow during extrusion. On the other hand, if the intrinsic viscosity of the polyester resin contained in the coating layer is more than 0.60 ⁇ / g, the pressure of the extruder is increased due to the increase in the viscosity of the melt during the manufacture of the multilayer polyester sheet, the film forming process may not be smooth, When the temperature of the extruder is raised to relieve the pressure rise, physical properties may decrease due to heat deformation.
• the multilayer polyester sheet is a polycondensation catalyst of lppm to 300 ppm, preferably 2 to 250 ppm content of the polyester resin contained in the coating layer, preferably from 2 to 250 ppm, preferably from 20 ppm to 20 ppm Polyester resins containing 200 ppm phosphorus stabilizer or lppm to 100 ppm cobalt-based colorant.
• the polycondensation catalyst may be used in the process of synthesizing the polyester resin contained in the coating layer, and examples of the polycondensation catalyst are not particularly limited. For example, a titanium compound, a tin compound, a germanium compound, and an antimony compound Or combinations thereof. If the amount of the central metal element is less than lppm, the desired degree of polymerization cannot be reached, and if it exceeds 300 ppm, the color of the final polymer may change or promote side reactions.
• titanium compound examples include tetraethyl titanate, acetyl tripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethyl nucleosil titanate, octylene glycol titanate, lactate titanate.
• tin-based compound examples include diaryl tin dihalide, dialkyl tin dihalide, diaryl tin oxide, tetrayryl tin compound, tin alkoxide, alkylin salt, alkyl tin compound, mixed alkyl aryl tin, and the like. have.
• germanium compound examples include germanium dioxide (Ge02), germanium tetrachloride (germanium tetrachloride, GeCl 4 ), germanium ethyleneglycoxide, germanium acetate, and copolymers using these, And combinations thereof.
• germanium dioxide may be used, and as such germanium dioxide, both crystalline and amorphous may be used, and glycol solubility may also be used.
• antimony-based compound examples include antimony oxide, antimony triacetate, copolymers using these, and mixtures thereof.
• the phosphorus stabilizer may be used in the process of synthesizing the polyester resin contained in the coating layer, and examples of the phosphorus stabilizer are not particularly limited, but specific examples thereof include phosphorous acid, phosphoric acid, trimethyl phosphate, triethyl phosphate, and triphenyl phosphate. Triethyl phosphono acetate and the like can be used. If the amount of the phosphorus stabilizer is less than lppm, it is difficult to obtain a desired bright color, and if the amount of the phosphorus stabilizer exceeds 100 ppm, the desired high degree of polymerization may not be reached.
• cobalt-based coloring agent may be used in the process of synthesizing the polyester resin contained in the coating layer, but examples of the cobalt-based coloring agent are not particularly limited, and specific examples include cobalt acetate and cobalt propionate. Can be.
• conventionally known organic compounds may be used as the colorant.
• the coating layer or the base layer may further include an additive including a sunscreen agent, an antioxidant, a lubricant, an antistatic crab, a layer reinforcing agent, a fine particle, or a combination of two or more thereof.
• an additive including a sunscreen agent, an antioxidant, a lubricant, an antistatic crab, a layer reinforcing agent, a fine particle, or a combination of two or more thereof.
• the method of adding the additive are not particularly limited, for example, the addition during the polymerization reaction Or a high concentration master batch of an additive is prepared and diluted and mixed.
• the method or apparatus that can be used in the production of the multilayer polyester sheet is not particularly limited, for example, by forming the base layer and the coating layer, and through the method of laminating or bonding each, or the like,
• the base layer and the coating layer may be formed and laminated at the same time. More specifically, a method of making a multi-layer sheet by melting each layer of the coating layer and the base layer with a different extruder and melt-laid using a multi-layer die, a method of melt-pushing each layer with a different extruder to melt-glued with The molded coating layer can be produced by heat bonding immediately after being pushed out by a T die of a base layer sheet extruder.
• a molded article including the above-described multilayer polyester sat may be provided.
• the multilayer polyester sheet of the above embodiment exhibits physical properties such as high heat resistance, chemical resistance, and impact resistance, and may have excellent appearance characteristics, and may be more easily controlled according to a use. Accordingly, the multilayer polyester sheet can be variously applied to fields such as packaging cases and thermoformed products of various products including foods.
• the molded article may be formed by various molding methods such as injection, extrusion, extrusion blow, injection blow and profile extrusion, and post-processing such as thermoforming using the same according to the application. It can be obtained by molding through. .
• the specific shape or size of the molded article may be determined according to the application thereof, and may be, for example, a shape of a sheet or a container, an area of 10 to 1000 cm 2 for a sheet, and a volume of 100 to 5000 cm 3 for a container. It may have, and both the sheet and the container may have a thickness of 0.01 to 0.4mm.
• Content about the molded article manufactured using the multilayer polyester sheet includes the above-described content with respect to the embodiment. ⁇ Effects of the Invention ⁇
• a multilayer polyester sheet exhibiting physical properties such as high heat resistance, chemical resistance and impact resistance, and having excellent appearance characteristics and more easily controlling physical properties required according to a use, and a molded article obtained from the multilayer polyester sheet Can be provided.
• Terephthalic acid, 1,4-cyclonucleic acid dimethanol and ethylene glycol were added in a molar ratio of 1: 0.3: 0.3 in a 7 L volume reaction vessel, and isosorbide was added to satisfy the following Table 1 content for the total diet. Combined and esterified at a pressure of 0.5 kg / cuf and 270 ° C.
• the coating layer composed of the polyester resin obtained through the esterification reaction and the polycondensation reaction and the substrate layer composed of various other polyester resins were melted by controlling the respective melting temperatures using a multilayer extruder, and laminated using the multilayer die.
• the multilayer polyester sheet was produced by the method.
• the molded article manufactured using the multilayer polyester sheet or the multilayer polyester sheet is pulverized, and impurities are removed while dehumidifying and drying at about 80 ° C.
• a polyester resin was obtained in the same manner as in Examples 1 to 5, except that the isosorbide content used in the reaction was changed.
• a type the multilayer polyester sheet. using
• a sample of (25 cm) x (15 cm) x (5 cm) size was prepared and placed in Convect i on oven made by Jio Tech Co., Ltd., and visually deformed for 60 minutes at a temperature of 90 ° C. The apparent deformation was visually determined by observing the difference in shape between the sample and the sample after putting it in the oven.
• the multilayer polyester sheet was stored at minus 20 ° C. for 60 minutes and then dropped from the liii height to determine whether it was broken.
• the multilayer polyester sheet was immersed at 60 ° C. for 30 hours in an ethanol solution, and then checked for appearance to confirm deformation.
• the polyester resin contained in the coating layer obtained in the above embodiment even if the content of the same isosorbide showed a characteristic that the glass transition temperature increases as the intrinsic viscosity increases. On the contrary, even with the same intrinsic viscosity, the glass transition temperature was increased with increasing isosorbide content.
• the multilayer polyester sheet obtained in the embodiment there is no deformation in Oven test A type, the deformation temperature is higher than 90 ° C in Oven test B type can realize excellent heat resistance as a material of heat-resistant food and packaging containers Appeared.
• the multilayer polyester sheet obtained in the Example isosorbide As the content and intrinsic viscosity increased, the delamination strength was excellent, and there was almost no deformation to ethanol or sunscreen.
• Example 6 as the base layer contains 40% by weight of recycled resin, the deformation temperature is increased at least rc or more in Oven test B type compared to Example 4, which does not include the recycled resin, It has been shown to have an effect of improving heat resistance.
• the glass transition temperature was shown to be lowered below 120 ° C.
• the multilayer polyester sheet obtained in the comparative example is deformed in the Oven test A type, the deformation temperature is lower than 80 ° C in the Oven test B type is enough heat resistance for use as a material of heat-resistant food and packaging containers It was confirmed that I could not

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• 2014
  • 2014-04-11 KR KR1020140043788A patent/KR102251210B1/ko active Active
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