WO2020218684A1 - Feuille de mousse comprenant des particules inorganiques et son procédé de fabrication - Google Patents

Feuille de mousse comprenant des particules inorganiques et son procédé de fabrication Download PDF

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Publication number
WO2020218684A1
WO2020218684A1 PCT/KR2019/011327 KR2019011327W WO2020218684A1 WO 2020218684 A1 WO2020218684 A1 WO 2020218684A1 KR 2019011327 W KR2019011327 W KR 2019011327W WO 2020218684 A1 WO2020218684 A1 WO 2020218684A1
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WIPO (PCT)
Prior art keywords
foam sheet
earth metal
alkaline earth
weight
equation
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Application number
PCT/KR2019/011327
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English (en)
Korean (ko)
Inventor
이광희
함진수
허미
김우진
하상훈
최종한
Original Assignee
주식회사 휴비스
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Priority claimed from KR1020190048407A external-priority patent/KR102196665B1/ko
Priority claimed from KR1020190048408A external-priority patent/KR102196666B1/ko
Application filed by 주식회사 휴비스 filed Critical 주식회사 휴비스
Priority to JP2020526376A priority Critical patent/JP2021524868A/ja
Priority to CN201980005712.3A priority patent/CN112166143B/zh
Publication of WO2020218684A1 publication Critical patent/WO2020218684A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a foam sheet in which inorganic particles containing an alkaline earth metal carbonate are dispersed in a polyester resin and a method of manufacturing the foam sheet.
  • Polyester resins having crystallinity such as polyethylene terephthalate (PET) are superior to polyethylene resins or polypropylene resins, and are used in various fields that require light weight and high physical properties due to excellent mechanical properties and excellent heat resistance and chemical resistance. This is possible. Polyester resin has excellent mechanical and chemical properties, so it can be applied for a variety of purposes, for example, drinking water containers and medical uses, food packaging, food containers, sheets, films, automobile molded products, etc. Applications are being made in the field of PET
  • a foam sheet containing a polyester resin has a foam layer composed of a resin composition containing a polyester resin, so it is excellent in light weight and strength, so that it can be used as a sheet-shaped molded body as it is, as well as three-dimensional It can be molded into a molded article having a typical shape.
  • the foam sheet comprising a polyester resin has the high rigidity of being excellent in light weight and strength as described above, and thus it is difficult to impart a desired shape by thermoforming or the like, and is easily broken. Therefore, development of a polyester foam sheet excellent in thermoformability is required.
  • the present invention is to provide a foam sheet in which inorganic particles containing an alkaline earth metal carbonate are dispersed in a polyester resin and a method of manufacturing the foam sheet.
  • the content of residual alkaline earth metal elements per unit area (1 m wide ⁇ 1 m long) of the foam sheet is in the range of 0.2 to 2% by weight And, it provides a foam sheet satisfying the following Equation 1:
  • y represents the thickness deviation rate of the foam sheet, the unit is %
  • x represents the content of alkaline earth metal elements per unit area of the foam sheet, and the unit is% by weight
  • a is 6.4 ⁇ a ⁇ 7.4, and b is 0.59 ⁇ b ⁇ 0.7.
  • the present invention includes the step of extruding and foaming a resin melt containing inorganic particles containing a polyester resin and an alkylritometallic carbonate with an extruder to prepare a foam sheet, and the foamed foam sheet is foamed.
  • the foamed sheet has a content of residual alkaline earth metal element per unit area (1 m wide ⁇ 1 m long) in the range of 0.2 to 2% by weight, and provides a method for producing a foam sheet satisfying the following Equation 1:
  • y represents the thickness deviation rate of the foam sheet, the unit is %
  • x represents the content of alkaline earth metal elements per unit area of the foam sheet, and the unit is% by weight
  • a is 6.4 ⁇ a ⁇ 7.4, and b is 0.59 ⁇ b ⁇ 0.7.
  • the content of residual alkaline earth metal elements per unit area (1 m wide ⁇ 1 m long) of the foam sheet is 0.2 to 2.0% by weight. Range, and a foam sheet having a constant thickness of 10% or less can be provided.
  • the foam sheet according to the present invention can reduce the cell size and increase the density of the foam sheet by including inorganic particles, and the sheet surface is uniform to reduce the occurrence of corrugation, and exhibit excellent thermoformability. I can.
  • 1 is a graph showing the thickness variation rate of foam sheets according to Examples and Comparative Examples of the present invention.
  • FIGS. 2A and 2B are photographs of a foam sheet with wrinkles according to a comparative example of the present invention and a foam sheet without wrinkles according to an embodiment of the present invention, respectively.
  • the foam sheet according to the present invention can provide a foam sheet having a constant thickness with a thickness deviation of 10% or less of the foam sheet by dispersing inorganic particles containing alkaline earth metal carbonate in a polyester resin.
  • the foam sheet according to the present invention contains alkaline earth metal carbonate as inorganic particles, the cell size of the foam sheet can be reduced, the density can be increased, and the sheet surface is uniform, so that the occurrence of corrugation can be reduced. , It can exhibit excellent thermoformability.
  • the present invention is a polyester foam sheet in which inorganic particles containing an alkylri earth metal carbonate are dispersed in a polyester resin, and the content of the residual alkaline earth metal element per unit area (1 m width ⁇ 1 m length) of the foam sheet is In the range of 0.2 to 2% by weight, it provides a foam sheet satisfying the following equation:
  • y represents the thickness deviation rate of the foam sheet, the unit is %
  • x represents the content of alkaline earth metal elements per unit area of the foam sheet, and the unit is% by weight
  • a is 6.4 ⁇ a ⁇ 7.4, and b is 0.59 ⁇ b ⁇ 0.7.
  • a is 6.6 ⁇ a ⁇ 7.4, 6.8 ⁇ a ⁇ 7.4, 7.0 ⁇ a ⁇ 7.4, 6.4 ⁇ a ⁇ 7.2, 6.4 ⁇ a ⁇ 7.0, 6.4 ⁇ a ⁇ 6.8, or 6.6 ⁇ a ⁇ 7.0 days
  • b is 0.61 ⁇ b ⁇ 0.7, 0.63 ⁇ b ⁇ 0.7, 0.65 ⁇ b ⁇ 0.7, 0.67 ⁇ b ⁇ 0.7, 0.59 ⁇ b ⁇ 0.68, 0.59 ⁇ b ⁇ 0.66, 0.59 ⁇ b ⁇ 0.64, or 0.60 ⁇ b ⁇ 0.65 may be.
  • the thickness variation rate (y in Equation 1) of the foam sheet according to the present invention may be 7 to 22%.
  • the thickness deviation rate of the foam sheet is 7 to 20%, 7 to 15%, 7 to 12%, 7 to 10%, 10 to 22%, 10 to 15%, 12 to 22%, or 15 to May be 22%.
  • the content of the residual alkaline earth metal element per unit area (1 m width ⁇ 1 m length) of the foam sheet or x in Equation 1 may be 0.2 to 2.0% by weight, respectively.
  • the content of residual alkaline earth metal elements per unit area of the foam sheet is 0.2 to 1.8% by weight, 0.2 to 1.6% by weight, 0.2 to 1.4% by weight, 0.2 to 1.2% by weight, 0.2 to 1.0% by weight, 0.2 to It may be 0.5% by weight, 0.5 to 2.0% by weight, 1.0 to 2.0% by weight, 1.2 to 2.0% by weight, or 1.5 to 2.0% by weight.
  • foaming may not occur.
  • the foam sheet may have an average foam density of 100 to 600 kg/m 3 according to KS M ISO 845:2012.
  • the average foam density of the foam sheet is 100 to 500 kg/m 3 , 100 to 400 kg/m 3 , 100 to 300 kg/m 3 , 100 to 200 kg/m 3 , 200 to 600 kg/m 3 , 300 to 600 kg/m 3 , 400 to 600 kg/m 3 , or 500 to 600 kg/m 3 .
  • the sheet surface may be uniform because no corrugation occurs in the foam sheet, and the KS M of the foam sheet at this time
  • the average foam density according to ISO 845:2012 may be 100 to 600 kg/m 3 .
  • the average thickness of the foam sheet may be in the range of 1.0 to 5.0 mm.
  • the average thickness of the foam sheet is 1.0 to 4.0 mm, 1.0 to 3.5 mm, 1.0 to 3.0 mm, 1.0 to 5.5 mm, 1.0 to 2.0 mm, 1.0 to 1.5 mm, 1.5 to 5.0 mm, 2.0 to 5.0 mm , 3.0 to 5.0 mm, or 4.0 to 5.0 mm.
  • the foam sheet according to the present invention includes an alkaline earth metal carbonate, so that the cell size of the foam sheet can be reduced and the density can be increased by the alkaline earth metal carbonate dispersed in the foam sheet, and to form and foam cells of a uniform size as a whole.
  • the alkaline earth metal carbonate is an inorganic particle, and by including the alkaline earth metal carbonate, the sheet surface may be uniform and excellent thermoformability may be exhibited.
  • the thermal conductivity of calcium carbonate may be 1.0 to 3.0 kcal/mh°C, so that the foam sheet containing calcium carbonate as described above exhibits excellent thermal conductivity. As a result, it has a uniform surface and can exhibit excellent thermoformability.
  • the thermal conductivity of the calcium carbonate may be 1.2 to 2.5 kcal/mh°C, 1.5 to 2.2 kcal/mh°C, or 1.8 to 2.0 kcal/mh°C. More specifically, the thermal conductivity of calcium carbonate may be 1.5 to 2.5 kcal/mh°C or 1.8 to 2.3 kcal/mh°C.
  • the alkaline earth metal element may be an inorganic carbonate containing at least one cation selected from the group consisting of Ca, Mg, and Ba.
  • the inorganic particles containing the alkaline earth metal carbonate may include calcium carbonate (CaCO 3 ), magnesium carbonate (MgCO 3 ), and barium carbonate (BaCO 3 ), and more specifically, the inorganic particles of the present invention It may contain calcium carbonate.
  • the content of inorganic particles per unit area of the foam sheet that is, the content of alkaline earth metal carbonate per unit area of the foam sheet can be determined by measuring the content of residual alkaline earth metal elements per unit area of the foam sheet.
  • the content of the alkaline earth metal element remaining in the foam sheet after the manufacture of the foam sheet compared to the amount of the inorganic particles containing the alkaline earth metal carbonate in the polyester resin may be 70 to 95%.
  • the content of the residual alkaline earth metal element relative to the input amount before the foam sheet is manufactured is 70 to 90%, 70 to 85%, 70 to 80%, 75 to 95%, 80 to 95%, 85 to 95%, or 90 To 95%.
  • the average size of the inorganic particles may be 1.0 to 5.0 ⁇ m.
  • the average particle size of the inorganic carbonate may be 1.0 to 4.0 ⁇ m, 1.0 to 3.0 ⁇ m, 1.0 to 2.0 ⁇ m, 2.0 to 5.0 ⁇ m, or 3.0 to 5.0 ⁇ m.
  • polyesters examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polylactic acid (PLA), and polyglycolic acid.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PLA polylactic acid
  • PGA polypropylene
  • PE polyethylene
  • PEA polyethylene adipate
  • PHA polyhydroxyalkanoate
  • PTT polytrimethylene terephthalate
  • PEN polyethylene naphthalate
  • the polyester foam sheet may be a polyethylene terephthalate (PET) foam sheet.
  • PET polyethylene terephthalate
  • The'corrugation' of the foam sheet means that the surface of the foam sheet is wrinkled in a rough or wavy shape.
  • the number of wrinkles of the foam sheet can be measured by visually checking the surface of the foam sheet, and may be 10 or less per unit area (1 m wide ⁇ 1 m long) of the foam sheet.
  • the wrinkles are 0 (no wrinkles) to 10, 0 to 8, 0 to 6, 0 to 4, or 0 to 2 per unit area (width 1 m ⁇ 1 m) of the foam sheet. It can be a dog.
  • the foam sheet may have an evaluation grade of 2 or less in a unit area when evaluating reliability for surface uniformity. For example, in the reliability evaluation of the surface uniformity, the foam sheet is cut into a width of 1 m ⁇ 1 m, and the number of wrinkles present on the cut sheet can be measured.
  • Grade 1 When the number of wrinkles is 0 / Grade 2: When the number of wrinkles is more than 0 and less than 2 / Grade 3: The number of wrinkles is more than 2) 4 or less / Grade 4: When the number of wrinkles is more than 4 and 10 or less / Grade 5: When the number of wrinkles is more than 10).
  • the foam sheet may have two or less wrinkles in a unit area.
  • the foam sheet according to the present invention includes alkaline earth metal carbonate as inorganic particles, so that the cell size of the foam sheet can be reduced, the density can be increased, and the sheet surface is uniform, so that the occurrence of corrugation can be reduced.
  • the foam sheet may be one that satisfies the following Equation 1 when evaluating the curl for a foam sheet having a width of 1 cm x 1 cm:
  • L chord represents the shortest distance between any point A present on the foam sheet and a point B 0.5 mm away from the point A, specifically, the "chord" length of the points A and B.
  • the distance between any point A present on the foam sheet and a point B (L chord ) 0.5 mm away from the point A may be reduced to less than 0.5 mm, but the foam sheet according to the present invention is 5
  • the distance reduced based on the mm foam sheet may be 0.1 mm or less.
  • the degree of warpage according to the warpage evaluation of the foam sheet according to the present invention is 0.1 mm or less, for example, 0 (no warpage occurs) to 0.1 mm, 0 to 0.08 mm, 0 to 0.05 mm, 0 to 0.03 mm , 0.03 to 0.1 mm, or may be 0.05 to 0.1 mm.
  • The'curl' of the foam sheet means that the foam sheet itself is bent, and the'corrugation' of the foam sheet means that the surface of the foam sheet is wrinkled in an uneven or wavy shape.
  • the foam sheet according to the present invention includes alkaline earth metal carbonate as inorganic particles, so that the cell size of the foam sheet can be reduced, the density can be increased, and the sheet surface is uniform, so that the occurrence of corrugation can be reduced.
  • the present invention also includes the step of extruding and foaming a resin melt containing inorganic particles containing a polyester resin and an alkylri earth metal carbonate with an extruder to prepare a foam sheet in one embodiment
  • the foamed sheet is a foamed sheet having a content of the residual alkaline earth metal element per unit area (1 m wide ⁇ 1 m long) in the range of 0.2 to 2% by weight, and provides a method for producing a foam sheet that satisfies the following Equation 1 do:
  • y represents the thickness deviation rate of the foam sheet, the unit is %
  • x represents the content of alkaline earth metal elements per unit area of the foam sheet, and the unit is% by weight
  • a is 6.4 ⁇ a ⁇ 7.4, and b is 0.59 ⁇ b ⁇ 0.7.
  • a is 6.6 ⁇ a ⁇ 7.4, 6.8 ⁇ a ⁇ 7.4, 7.0 ⁇ a ⁇ 7.4, 6.4 ⁇ a ⁇ 7.2, 6.4 ⁇ a ⁇ 7.0, 6.4 ⁇ a ⁇ 6.8, or 6.6 ⁇ a ⁇ 7.0 days
  • b is 0.61 ⁇ b ⁇ 0.7, 0.63 ⁇ b ⁇ 0.7, 0.65 ⁇ b ⁇ 0.7, 0.67 ⁇ b ⁇ 0.7, 0.59 ⁇ b ⁇ 0.68, 0.59 ⁇ b ⁇ 0.66, 0.59 ⁇ b ⁇ 0.64, or 0.60 ⁇ b ⁇ 0.65 may be.
  • the thickness deviation rate of the foam sheet according to the present invention may be 7 to 22%.
  • the thickness deviation rate of the foam sheet is 7 to 20%, 7 to 15%, 7 to 12%, 7 to 10%, 10 to 22%, 10 to 15%, 12 to 22%, or 15 to May be 22%.
  • the content of the residual alkaline earth metal element per unit area (1 m wide ⁇ 1 m long) of the foam sheet may be 0.2 to 2.0% by weight.
  • the content of residual alkaline earth metal elements per unit area of the foam sheet is 0.2 to 1.8% by weight, 0.2 to 1.6% by weight, 0.2 to 1.4% by weight, 0.2 to 1.2% by weight, 0.2 to 1.0% by weight, 0.2 to It may be 0.5% by weight, 0.5 to 2.0% by weight, 1.0 to 2.0% by weight, 1.2 to 2.0% by weight, or 1.5 to 2.0% by weight.
  • the foam sheet may have an average foam density of 100 to 600 kg/m 3 according to KS M ISO 845:2012.
  • the average foam density of the foam sheet is 100 to 500 kg/m 3 , 100 to 400 kg/m 3 , 100 to 300 kg/m 3 , 100 to 200 kg/m 3 , 200 to 600 kg/m 3 , 300 to 600 kg/m 3 , 400 to 600 kg/m 3 , or 500 to 600 kg/m 3 .
  • the sheet surface may be uniform because no corrugation occurs in the foam sheet, and the KS M of the foam sheet at this time
  • the average foam density according to ISO 845:2012 may be 100 to 600 kg/m 3 .
  • the polyester resin and calcium carbonate introduced into the extruder may be added to the extruder, melted, and extruded to form a foam sheet.
  • a mixture of polyester resin chips and calcium carbonate may be melted to perform extrusion foaming.
  • the process of melting the polyester resin and calcium carbonate may be performed at a temperature of 260 to 300°C.
  • the inorganic particles containing the alkaline earth metal carbonate may be mixed with a polyester resin in the form of a master batch to prepare a resin melt.
  • the polyester resin in the step of introducing the polyester resin into the extruder, may have a shape such as a pellet, granule, bead, chip, etc. Thus, it can be introduced into the extruder in powder form.
  • the temperature of the extruded foamed sheet may be in the range of 220 to 270°C.
  • the temperature of the extruded foam sheet refers to the temperature of the foam sheet extruded between the extrusion die and the mandrel of the foaming device when extruded into a resin melt foam sheet using a foaming device. I can.
  • the temperature of the extruded foamed sheet may be 220 to 250°C, 220 to 230°C, 230 to 270°C, or 250 to 270°C.
  • the cell size of the foam sheet can be reduced, the density can be increased, the sheet surface is uniform, so that the occurrence of corrugation can be reduced, and excellent thermoformability Can represent.
  • the foam sheet obtained by extruding the resin has a high thermal conductivity, so that the foam sheet may be torn during foam sheet molding.
  • the alkaline earth metal element may be an inorganic carbonate containing at least one cation selected from the group consisting of Ca, Mg, and Ba.
  • the inorganic particles containing the alkaline earth metal carbonate may include calcium carbonate (CaCO 3 ), magnesium carbonate (MgCO 3 ), and barium carbonate (BaCO 3 ), and more specifically, the inorganic particles of the present invention It may contain calcium carbonate.
  • the content of inorganic particles per unit area of the foam sheet that is, the content of alkaline earth metal carbonate per unit area of the foam sheet can be determined by measuring the content of residual alkaline earth metal elements per unit area of the foam sheet.
  • the content of the alkaline earth metal element remaining in the foam sheet after the manufacture of the foam sheet compared to the amount of the inorganic particles containing the alkaline earth metal carbonate in the polyester resin may be 70 to 95%.
  • the content of the residual alkaline earth metal element relative to the input amount before the foam sheet is manufactured is 70 to 90%, 70 to 85%, 70 to 80%, 70 to 85%, 70 to 80%, 75 to 95%, 80 to 95%, 85 to 95%, or 90 to 95%.
  • the average size of the inorganic particles may be 1.0 to 5.0 ⁇ m.
  • the average particle size of the inorganic carbonate may be 1.0 to 4.0 ⁇ m, 1.0 to 3.0 ⁇ m, 1.0 to 2.0 ⁇ m, 2.0 to 5.0 ⁇ m, or 3.0 to 5.0 ⁇ m.
  • the method of measuring the residual inorganic carbonate content per unit area of the foam sheet may be to pretreat the foam sheet in an acidic solvent and then measure it through cation analysis with an atomic absorption spectrophotometer.
  • the method of manufacturing a foam sheet according to the present invention can produce a foam sheet having an average thickness deviation of 15% or less. Specifically, the method of manufacturing a foam sheet according to the present invention can produce a foam sheet having an average thickness deviation of 12% or less, 10% or less, 8% or less, 7% or less, or 5% or less. More specifically, the method of manufacturing a foam sheet according to the present invention can produce a foam sheet showing an average thickness deviation of 1 to 10% or 5 to 8%.
  • the method of manufacturing a polyester foam sheet according to the present invention is a process of heat-treating the polyester foam sheet to post-foaming, thereby reducing the volume change rate when heat is applied to the polyester foam sheet to prevent post-foaming. It can be prevented, and as the thickness of the polyester foam sheet increases due to post-foaming, the degree of crystallinity increases and the flexural strength may increase.
  • the surface temperature and heat treatment time of the foam sheet according to the heat treatment may affect the thickness of the polyester foam sheet, and by heat treatment in the heat treatment temperature and time range according to the present invention
  • the crystallinity, heat resistance and flexural strength of the polyester foam sheet can be improved.
  • the step of heat-treating the extruded foamed polyester foam sheet may be heat treatment for 30 to 200 seconds, for example, the heat treatment may be 30 to 200 seconds, 30 to 150 seconds, 30 to 100 seconds, 30 to 50 Second, it may be performed for 50 to 200 seconds, 100 to 200 seconds, or 150 to 200 seconds.
  • the step of heat-treating the extruded foamed polyester foam sheet may be to prepare a polyester foam sheet having a surface temperature of 120 to 250°C by heat treatment, for example, the surface temperature is 120 to 250°C, 120 To 230°C, 120 to 200°C, 120 to 180°C, 120 to 160°C, 120 to 140°C, 140 to 250°C, 160 to 250°C, 180 to 250°C, 200 to 250°C, or 230 to 250°C I can.
  • the step of heat treating the extruded foamed polyester foam sheet may include a direct heat treatment and an indirect heat treatment method, for example, direct heat treatment may be to apply heat directly to the surface of the foam sheet, and indirect heat treatment may be a heat treatment It may be to apply heat by controlling the temperature of the atmosphere.
  • the direct heat treatment may be heating the surface temperature of the extruded foamed polyester foam sheet to a temperature of 120 to 300°C.
  • the surface temperature of the extruded foamed polyester foam sheet may be heated to a temperature of 120 to 300°C, 120 to 200°C, 120 to 150°C, 150 to 300°C, or 200 to 300°C.
  • Heat treatment by contacting one or both sides of the extruded foamed polyester foam sheet to heat the surface temperature of the extruded polyester foam sheet to a temperature of 120 to 300°C, and one or both sides of the polyester foam sheet
  • the heating plate temperature to be heated may range from 100 to 300°C, 100 to 250°C, 100 to 200°C, 100 to 150°C, 150 to 300°C, 200 to 300°C, and 250 to 300°C.
  • the heat treatment of the extruded foamed polyester foam sheet may be heat treatment in an atmosphere of 120 to 600°C.
  • the extruded polyester foam sheet is extruded and foamed by heat treatment in an atmosphere of 120 to 600°C, 120 to 400°C, 120 to 200°C, 150 to 600°C, 200 to 600°C, or 400 to 600°C It may be to heat the surface temperature of the polyester foam sheet to a temperature of 120 to 300 °C.
  • the extruded polyester foam sheet according to the present invention When the heat treatment temperature of the extruded polyester foam sheet according to the present invention is performed within the above range, the extruded polyester foam sheet may be easily expanded after 1.5 to 3 times.
  • the expansion ratio may be 1.5 to 3 times the expansion ratio before the heat treatment.
  • the heat treatment may be to perform post-foaming of the extruded foamed polyester foam sheet, and may be expanded 1.5 to 3 times more than the expansion ratio before post-foaming (heat treatment).
  • the average thickness of the polyester foam sheet may be 1.5 to 10 mm.
  • the average thickness of the polyester foam sheet may be 1.5 to 2 times greater than before heat treatment of the extruded polyester foam sheet, for example, the average thickness of the polyester foam sheet is 1.5 to 10 mm, 1.5 to 8 mm , 1.5 to 5 mm, 5 to 10 mm, or 7.5 to 10 mm.
  • the expansion ratio of the polyester foam sheet is increased, and when heat is applied to the manufactured polyester foam sheet, post-foaming occurs and the shape is prevented from being deformed. can do.
  • the compressed foamed polyester foam sheet can be heated by passing through a heater by a conveyor belt to be heat treated (post foamed), and the compressed foamed polyester foam sheet is a nip roller that holds the front and rear ends in parallel. It can be heat treated (post-foaming) by being heated while passing through the heater by (Nip Roller).
  • the step of cooling the polyester foam sheet may be further performed.
  • the cooling step may be cooled by a cooling roller while the polyester foam sheet is moved by a conveyor belt.
  • the step of cooling may be performed to harden a portion in which the polyester foam sheet has been melted by heat treatment, and thereby prevent the shape of the polyester foam sheet from being distorted.
  • the temperature of the cooling roller is 15° C. or less, 1 to 14.5° C., 1.5 to 14° C., 2 to 13.5° C. 2.5 to 13° C., 3 to 12.5° C., 3.5 to 12° C., 4 To 11.5°C or 4.5 to 10°C.
  • the step of cutting the polyester foam sheet at regular intervals may be further performed.
  • the cutting step may be cut by a cutter while the polyester foam sheet is moved by a conveyor belt.
  • the polyester foam sheet may be cooled by passing a cooling roller while being moved by a conveyor belt and then cooled by a cutter while moving by a conveyor belt.
  • the manufacturing method of the polyester foam sheet according to the present invention has the advantage of improving processability and easy mass production by performing a process of cutting the heat-treated extruded foamed polyester foam sheet by a cutter.
  • additives may be added. If necessary, the additive may be introduced into the fluid connection line or added during the foaming process.
  • additives may have barrier performance, hydrophilization or waterproof function, and thickeners, surfactants, hydrophilic agents, heat stabilizers, waterproofing agents, cell size enlargers, infrared attenuators, plasticizers, fire protection chemicals, It may contain one or more functional additives selected from the group consisting of pigments, elastic polymers, extrusion aids, antioxidants, nucleating agents, anti-rotation agents and UV absorbers.
  • the foam sheet manufacturing method of the present invention may add one or more of a thickener, a nucleating agent, a thermal stabilizer, and a foaming agent, and may further include one or more of the functional additives listed above.
  • the steps of preparing the foam sheet of the present invention include a thickener, a hydrophilic agent, a heat stabilizer, a waterproof agent, a cell size enlarger, an infrared attenuator, a plasticizer, a fire protection chemical, a pigment, an elastic polymer, an extrusion aid, an antioxidant,
  • One or more additives selected from the group consisting of anti-slip agents and UV absorbers may be introduced into the fluid connection line.
  • additives not added to the fluid connection line may be added during the extrusion process.
  • the thickener is not particularly limited, but in the present invention, for example, pyromellitic dianhydride (PMDA) may be used.
  • PMDA pyromellitic dianhydride
  • the heat stabilizer may be an organic or inorganic compound.
  • the organic or inorganic compound may be, for example, phosphoric acid and its organic ester, phosphorous acid and its organic ester.
  • the heat stabilizer is a commercially available material, and may be phosphoric acid, alkyl phosphate or aryl phosphate.
  • the thermal stabilizer may be triphenyl phosphate, but is not limited thereto, and as long as it can improve the thermal stability of the resin foam sheet, it can be used without limitation within a conventional range.
  • blowing agent a physical blowing agent such as N 2 , CO 2 , freon, butane, pentane, neopentane, hexane, isohexane, heptane, isoheptane, methyl chloride, etc.
  • a physical blowing agent such as N 2 , CO 2 , freon, butane, pentane, neopentane, hexane, isohexane, heptane, isoheptane, methyl chloride, etc.
  • the waterproofing agent is not particularly limited, and for example, silicone-based, epoxy-based, cyanoacrylic acid-based, polyvinyl acrylate-based, ethylene vinyl acetate-based, acrylate-based, polychloroprene-based, polyurethane resin and polyester resin And a mixture of a mixture of polyol and a polyurethane resin, a mixture of acrylic polymer and polyurethane resin, a polyimide series, and a mixture of cyanoacrylate and urethane.
  • the present invention provides a food container comprising the foam sheet.
  • the food container according to the present invention includes inorganic carbonate as inorganic particles, so that the surface of the food container is uniform and the defect rate may be low during manufacture.
  • PET polyethylene terephthalate
  • Irganox Irganox
  • a PET foam sheet having an average thickness of 1.0 mm was prepared in the same manner as in Example 1, except that 1.9 parts by weight of calcium carbonate were mixed, and the density of the prepared PET foam sheet was 280 kg/m 3 .
  • a PET foam sheet having an average thickness of 2.2 mm was prepared in the same manner as in Example 1, except that 1.7 parts by weight of calcium carbonate were mixed, and the density of the prepared PET foam sheet was 240 kg/m 3 .
  • a PET foam sheet having an average thickness of 2.0 mm was prepared in the same manner as in Example 1, except for mixing 1.5 parts by weight of calcium carbonate, and the density of the prepared PET foam sheet was 200 kg/m 3 .
  • a PET foam sheet having an average thickness of 2.0 mm was prepared in the same manner as in Example 1, except for mixing 5.5 parts by weight of calcium carbonate, and the density of the prepared PET foam sheet was 350 kg/m 3 .
  • a PET foam sheet having an average thickness of 2.0 mm was prepared in the same manner as in Example 1, except for mixing 0.4 parts by weight of calcium carbonate, and the density of the prepared PET foam sheet was 200 kg/m 3 .
  • Each foam sheet was put in an electric furnace at 800° C. and incinerated for 3 hours, and the remaining amount was pretreated with an acidic solvent and then measured with an atomic absorption spectrometer (AAS). Specifically, the pretreatment was performed by dissolving an aerated sample with 3 mL of 36% hydrochloric acid and 1 mL of 60% nitric acid, filtering it with a 3 ⁇ m filter paper, taking it into a 100 mL flask, and filling it with distilled water to the mark. The solution was measured for Ca element content using an atomic absorption spectrophotometer (Varian, SpectrAA-30), and the measured value was obtained through a calibration curve. The calibration curve was obtained using a Ca standard solution (Kanto Chemical Co., Ltd., Ca 1,000 ppm).
  • the total width of each foam sheet was divided into 8 at regular intervals, and the thickness was measured using an indicator (ID-C112, MItutoyo), and the average value was calculated.
  • Equation 1 representing the thickness deviation of the foam sheet was derived using the measured values of Examples 1 to 4 and Comparative Example 1, and a graph thereof is shown in FIG. 1.
  • Each foam sheet was cut into a width of 1 m x a length of 1 m, the number of wrinkles present on the cut sheet was counted, and the number of counted wrinkles was classified according to the following criteria to evaluate the grade:
  • Grade 2 When the number of wrinkles exceeds 0 and 2 or less
  • Grade 3 When the number of wrinkles is more than 2 and 4 or less
  • Grade 4 When the number of wrinkles is more than 4 and not more than 10
  • Each foam sheet was cut to a width of 1.0 cm ⁇ 1.0 cm, and the cut sheets were fixed on an ultrahigh accurate 3-D profilometer (UA3P-300, Panasonic Corporation). Thereafter, the shortest distance between any point A existing on the fixed sheet and a point B 0.5 mm away from the point A (specifically, the "string" length of the point A and the point B) is measured, and the following Equation 1 was used to evaluate the surface uniformity of the foam sheet. At this time, the measurement temperature was 23°C, the relative humidity was 60%, and the vibration acceleration during the measurement was 0.5 cm/s 2 .
  • the degree of deflection of the foam sheet ⁇ L chord -0.5 mm ⁇
  • L chord represents the shortest distance between any point A present on the foam sheet and a point B 0.5 mm away from the point A.
  • the moldability test was conducted by heating the upper part of the heater to 400°C and the lower part to 320°C. When the surface temperature of the foam sheet reaches 155°C to 160°C (see Table 1 below for detailed temperature), the mold is molded with a temperature of 80°C. Thus, the degree of molding of the foam sheet was observed.
  • Comparative Example 1 contained a large amount of calcium carbonate (5.5% by weight), so that wrinkles (20 pieces) occurred in the sheet in the foaming process, and the thickness deviation was found to be 24%. The number of wrinkles was measured by visually checking the wrinkles formed in the foam sheet.
  • FIGS. 2A and 2B are photographs of a foam sheet with wrinkles according to a comparative example of the present invention (Comparative Example) and a foam sheet without wrinkles according to an embodiment of the present invention, respectively.
  • the foam sheet according to the present invention may contain a certain amount of calcium carbonate even after the production of the foam sheet by including calcium carbonate in a certain amount. Accordingly, wrinkles are not formed in the foam sheet manufacturing process and the foam sheet It can be seen that the thickness is constant and moldability is excellent during molding.
  • the content of residual alkaline earth metal elements per unit area (1 m wide ⁇ 1 m long) of the foam sheet is 0.2 to 2.0% by weight. Range, it is possible to provide a foam sheet having a constant thickness with a thickness deviation of 10% or less of the foam sheet.
  • the foam sheet according to the present invention can reduce the cell size and increase the density of the foam sheet by including inorganic particles, and the sheet surface is uniform to reduce the occurrence of corrugation, and exhibit excellent thermoformability. I can.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

La présente invention concerne une feuille de mousse de polyester dans laquelle des particules inorganiques contenant un carbonate de métal alcalino-terreux sont dispersées dans une résine de polyester, la quantité d'éléments de métal alcalino-terreux résiduels par unité de surface (1 m de large × 1 m de long) de la feuille de mousse est comprise entre 0,2 et 2,0 % en poids, et la feuille de mousse a une épaisseur fixe dans laquelle l'écart d'épaisseur est compris entre 7 et 22 %.
PCT/KR2019/011327 2019-04-25 2019-09-03 Feuille de mousse comprenant des particules inorganiques et son procédé de fabrication WO2020218684A1 (fr)

Priority Applications (2)

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JP2020526376A JP2021524868A (ja) 2019-04-25 2019-09-03 無機粒子を含む発泡シートおよびその製造方法
CN201980005712.3A CN112166143B (zh) 2019-04-25 2019-09-03 包含无机粒子的发泡片及其制造方法

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KR10-2019-0048407 2019-04-25
KR1020190048407A KR102196665B1 (ko) 2019-04-25 2019-04-25 무기입자를 포함하는 발포시트 및 이의 제조방법
KR1020190048408A KR102196666B1 (ko) 2019-04-25 2019-04-25 무기입자를 포함하는 발포시트 및 이의 제조방법
KR10-2019-0048408 2019-04-25

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EP2612881A1 (fr) * 2012-01-05 2013-07-10 Omya Development AG Agents de remplissage pour produits de polymère rigides en mousse
KR20150078004A (ko) * 2013-12-30 2015-07-08 도레이케미칼 주식회사 기계적 강도 및 발포율이 향상된 미세기공 열가소성 고분자 수지 발포체 및 이의 제조방법
KR20150099390A (ko) * 2012-12-21 2015-08-31 닛토덴코 가부시키가이샤 수지 발포체 및 발포 시일재
KR20190012349A (ko) * 2017-07-27 2019-02-11 주식회사 휴비스 스킨층을 포함하는 발포시트, 이의 제조방법 및 이를 포함하는 식품 용기

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JPS5940162B2 (ja) * 1977-04-13 1984-09-28 株式会社クラレ ポリエステル発泡成形物およびその製造法
GB8402514D0 (en) * 1984-01-31 1984-03-07 Scott Bader Co Unsaturated polyester foams
EP1367088A4 (fr) * 2001-07-11 2004-07-07 Kaneka Corp Composition de resine polyester expansible
JP2003026845A (ja) * 2001-07-11 2003-01-29 Kanegafuchi Chem Ind Co Ltd 発泡性ポリエステル樹脂組成物
JP6901553B2 (ja) * 2018-06-29 2021-07-14 フュービス・コーポレイションＨｕｖｉｓ Ｃｏｒｐｏｒａｔｉｏｎ 炭酸カルシウムを含む発泡シート、その製造方法およびこれを含む食品容器

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KR0118112B1 (ko) * 1988-12-01 1997-09-30 마쓰다 쇼헤이 열가소성 폴리에스테르계 수지 발포체의 제조방법
EP2612881A1 (fr) * 2012-01-05 2013-07-10 Omya Development AG Agents de remplissage pour produits de polymère rigides en mousse
KR20150099390A (ko) * 2012-12-21 2015-08-31 닛토덴코 가부시키가이샤 수지 발포체 및 발포 시일재
KR20150078004A (ko) * 2013-12-30 2015-07-08 도레이케미칼 주식회사 기계적 강도 및 발포율이 향상된 미세기공 열가소성 고분자 수지 발포체 및 이의 제조방법
KR20190012349A (ko) * 2017-07-27 2019-02-11 주식회사 휴비스 스킨층을 포함하는 발포시트, 이의 제조방법 및 이를 포함하는 식품 용기

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