WO2020218684A1 - Foam sheet comprising inorganic particles, and manufacturing method therefor - Google Patents

Foam sheet comprising inorganic particles, and manufacturing method therefor 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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WO
WIPO (PCT)
Prior art keywords
foam sheet
earth metal
alkaline earth
weight
equation
Prior art date
Application number
PCT/KR2019/011327
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French (fr)
Korean (ko)
Inventor
이광희
함진수
허미
김우진
하상훈
최종한
Original Assignee
주식회사 휴비스
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from KR1020190048407A external-priority patent/KR102196665B1/en
Priority claimed from KR1020190048408A external-priority patent/KR102196666B1/en
Application filed by 주식회사 휴비스 filed Critical 주식회사 휴비스
Priority to JP2020526376A priority Critical patent/JP2021524868A/en
Priority to CN201980005712.3A priority patent/CN112166143B/en
Publication of WO2020218684A1 publication Critical patent/WO2020218684A1/en

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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.

Abstract

The present invention relates to a polyester foam sheet in which inorganic particles containing an alkaline earth metal carbonate are dispersed in a polyester resin, wherein the amount of residual alkaline earth metal elements per unit area (1 m width × 1 m length) of the foam sheet is 0.2-2.0 wt%, and the foam sheet has a fixed thickness in which the deviation of thickness is 7-22%.

Description

무기입자를 포함하는 발포시트 및 이의 제조방법Foam sheet containing inorganic particles and method for manufacturing the same
본 발명은 폴리에스테르 수지에 알칼리토금속 탄산염을 함유하는 무기입자가 분산된 발포시트 및 상기 발포시트의 제조방법에 관한 것이다.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.
폴리에틸렌 테레프탈레이트(PET) 등의 결정성을 가지는 폴리에스테르 수지는 폴리에틸렌계 수지나 폴리프로필렌계 수지 등에 비해 기계적 특성이 우수하고 내열성 및 내화학성 등이 뛰어나 경량 및 높은 물리적 특성이 요구되는 각종 분야에서 활용이 가능하다. 폴리에스테르 수지(polyester resin)는 기계적 특성 및 화학적 특성이 우수하여 다용도로의 응용, 예를 들면 종래부터 음용수 용기 및 의료용, 식품 포장지, 식품 용기, 시트(sheet), 필름(film), 자동차 성형품 등의 분야에 응용이 이루어지고 있다. 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
특히, 폴리에스테르 수지를 포함하는 발포시트는 폴리에스테르계 수지를 포함한 수지 조성물로 구성되는 발포층을 가짐으로써 경량성과 강도가 우수해 그대로 시트형 성형체로서 이용 가능할 뿐만 아니라, 열 성형을 실시하는 등 3차원적인 형상을 가지는 성형체로 성형 가공할 수 있다.In particular, 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.
그러나, 폴리에스테르 수지를 포함하는 발포 시트는 상기와 같이 경량성과 강도가 우수한 것의 고강성을 가짐으로써 열 성형 등에 의해 원하는 형상을 부여하는 것이 어려고, 잘 깨지는 단점이 있다. 따라서, 열 성형성이 우수한 폴리에스테르 발포시트의 개발이 요구되고 있다. However, 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.
본 발명은 폴리에스테르 수지에 알칼리토금속 탄산염을 함유하는 무기입자가 분산된 발포시트 및 상기 발포시트의 제조방법을 제공하고자 한다.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.
상기 과제를 해결하기 위하여,In order to solve the above problem,
본 발명은 일실시예에서, The present invention in one embodiment,
폴리에스테르 수지에 알킬리토금속 탄산염을 함유하는 무기입자가 분산된 폴리에스테르 발포시트로서, 발포시트의 단위 면적(가로 1 m × 세로 1 m) 당 잔류 알칼리토금속 원소의 함량이 0.2 내지 2 중량% 범위이며, 하기 수학식 1을 만족하는 발포시트를 제공한다:As a polyester foam sheet in which inorganic particles containing an alkylri earth metal carbonate are dispersed in a polyester resin, 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:
[수학식 1][Equation 1]
y=a(x-b)2+7.3691y=a(xb) 2 +7.3691
수학식 1에서,In Equation 1,
y는 발포시트의 두께 편차율을 나타내고, 단위는 %이며, y represents the thickness deviation rate of the foam sheet, the unit is %,
x는 발포시트의 단위 면적당 알칼리토금속 원소의 함량을 나타내고, 단위는 중량%이며,x represents the content of alkaline earth metal elements per unit area of the foam sheet, and the unit is% by weight,
a는 6.4≤a≤7.4이고, b는 0.59≤b≤0.7이다.a is 6.4≤a≤7.4, and b is 0.59≤b≤0.7.
또한, 본 발명은 일실시예에서, 폴리에스테르 수지 및 알킬리토금속 탄산염을 함유하는 무기입자를 포함하는 수지 용융물을 압출기로 압출 발포하며 발포시트를 제조하는 단계를 포함하고, 발포된 발포시트는 발포된 발포시트는 단위 면적(가로 1 m × 세로 1 m) 당 잔류 알칼리토금속 원소의 함량이 0.2 내지 2 중량% 범위이며, 하기 수학식 1을 만족하는 발포시트의 제조방법을 제공한다:In addition, in one embodiment, 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:
[수학식 1][Equation 1]
y=a(x-b)2+7.3691y=a(xb) 2 +7.3691
수학식 1에서,In Equation 1,
y는 발포시트의 두께 편차율을 나타내고, 단위는 %이며,y represents the thickness deviation rate of the foam sheet, the unit is %,
x는 발포시트의 단위 면적당 알칼리토금속 원소의 함량을 나타내고, 단위는 중량%이며,x represents the content of alkaline earth metal elements per unit area of the foam sheet, and the unit is% by weight,
a는 6.4≤a≤7.4이고, b는 0.59≤b≤0.7이다.a is 6.4≤a≤7.4, and b is 0.59≤b≤0.7.
본 발명에 따른 발포시트는 폴리에스테르 수지에 알칼리토금속 탄산염을 함유하는 무기입자를 분산시킴으로써, 발포시트의 단위 면적(가로 1 m × 세로 1 m) 당 잔류 알칼리토금속 원소의 함량이 0.2 내지 2.0 중량% 범위이며, 발포시트의 두께 편차가 10% 이하로 일정한 두께를 갖는 발포시트를 제공할 수 있다. In the foam sheet according to the present invention, by dispersing inorganic particles containing alkaline earth metal carbonate in a polyester resin, 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.
본 발명에 따른 발포시트는 무기입자를 포함함으로써 발포시트의 셀의 사이즈는 줄이고, 밀도는 높일 수 있으며, 시트표면이 균일하여 주름(corrugation)의 발생을 감소시킬 수 있으며, 우수한 열 성형성을 나타낼 수 있다. 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.
도 1은 본 발명의 실시예 및 비교예에 따른 발포시트의 두께 편차율을 나타낸 그래프이다.1 is a graph showing the thickness variation rate of foam sheets according to Examples and Comparative Examples of the present invention.
도 2a 및 도 2b는 각각 본 발명의 비교예에 따른 주름이 발생한 발포시트 및 본 발명의 실시예에 따른 주름이 발생하지 않은 발포시트의 사진이다.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.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 특정 실시예들을 도면에 예시하고 상세한 설명에 구체적으로 설명하고자 한다.In the present invention, various modifications may be made and various embodiments may be provided, and specific embodiments will be illustrated in the drawings and described in detail in the detailed description.
그러나, 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.However, this is not intended to limit the present invention to a specific embodiment, it is to be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.
본 발명에서, "포함한다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.In the present invention, terms such as "comprises" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or a combination thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof, does not preclude in advance.
이하, 본 발명에 대하여 구체적으로 설명하기로 한다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 발포시트는 폴리에스테르 수지에 알칼리토금속 탄산염을 함유하는 무기입자를 분산시킴으로써, 발포시트의 두께 편차 10% 이하로 두께가 일정한 두께를 갖는 발포시트를 제공할 수 있다. 또한, 본 발명에 따른 발포시트는 무기입자로 알칼리토금속 탄산염을 포함함으로써, 발포시트의 셀의 사이즈는 줄이고, 밀도는 높일 수 있으며, 시트표면이 균일하여 주름(corrugation)의 발생을 감소시킬 수 있으며, 우수한 열 성형성을 나타낼 수 있다.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. In addition, since 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.
구체적으로, 본 발명은 폴리에스테르 수지에 알킬리토금속 탄산염을 함유하는 무기입자가 분산된 폴리에스테르 발포시트로서, 발포시트의 단위 면적(가로 1 m × 세로 1 m) 당 잔류 알칼리토금속 원소의 함량이 0.2 내지 2 중량% 범위이며, 하기 수학식 1을 만족하는 발포시트를 제공한다:Specifically, 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:
[수학식 1][Equation 1]
y=a(x-b)2+7.3691y=a(xb) 2 +7.3691
수학식 1에서,In Equation 1,
y는 발포시트의 두께 편차율을 나타내고, 단위는 %이며, y represents the thickness deviation rate of the foam sheet, the unit is %,
x는 발포시트의 단위 면적당 알칼리토금속 원소의 함량을 나타내고, 단위는 중량%이며,x represents the content of alkaline earth metal elements per unit area of the foam sheet, and the unit is% by weight,
a는 6.4≤a≤7.4이고, b는 0.59≤b≤0.7이다.a is 6.4≤a≤7.4, and b is 0.59≤b≤0.7.
예를 들어, 상기 a는 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, 또는 6.6≤a≤7.0일 수 있고, b는 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, 또는 0.60≤b≤0.65일 수 있다.For example, 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 And 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.
본 발명에 따른 발포시트의 두께 편차율(수학식 1의 y)은 7 내지 22%일 수 있다. 예를 들어, 상기 발포시트의 두께 편차율은 7 내지 20%, 7 내지 15%, 7 내지 12%, 7 내지 10%, 10 내지 22%, 10 내지 15%, 12 내지 22%, 또는 15 내지 22%일 수 있다.The thickness variation rate (y in Equation 1) of the foam sheet according to the present invention may be 7 to 22%. For example, 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%.
상기 발포시트의 단위 면적(가로 1 m × 세로 1 m) 당 잔류 알칼리토금속 원소의 함량 또는 수학식 1의 x는 각각 0.2 내지 2.0 중량%일 수 있다. 예를 들어, 상기 발포시트의 단위 면적 당 잔류 알칼리토금속 원소의 함량은 0.2 내지 1.8 중량%, 0.2 내지 1.6 중량%, 0.2 내지 1.4 중량%, 0.2 내지 1.2 중량%, 0.2 내지 1.0 중량%, 0.2 내지 0.5 중량%, 0.5 내지 2.0 중량%, 1.0 내지 2.0 중량%, 1.2 내지 2.0 중량%, 또는 1.5 내지 2.0 중량%일 수 있다. 상기 발포시트의 단위 면적 당 잔류 알칼리토금속 원소의 함량이 0.2 중량% 이하일 경우, 발포가 되지 않을 수 있다.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. For example, 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. When the content of the residual alkaline earth metal element per unit area of the foam sheet is 0.2% by weight or less, foaming may not occur.
상기 발포시트의 KS M ISO 845:2012에 따른 평균 발포 밀도는 100 내지 600 kg/m3일 수 있다. 예를 들어, 상기 발포시트의 평균 발포 밀도는 100 내지 500 kg/m3, 100 내지 400 kg/m3, 100 내지 300 kg/m3, 100 내지 200 kg/m3, 200 내지 600 kg/m3, 300 내지 600 kg/m3, 400 내지 600 kg/m3, 또는 500 내지 600 kg/m3일 수 있다.The foam sheet may have an average foam density of 100 to 600 kg/m 3 according to KS M ISO 845:2012. For example, 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 .
상기 발포시트의 단위 면적 당 잔류 알칼리토금속 원소의 함량이 0.2 내지 2.0 중량% 범위일 때, 발포시트에 주름(corrugation)이 발생하지 않아 시트표면이 균일할 수 있으며, 이 때의 발포시트의 KS M ISO 845:2012에 따른 평균 발포 밀도가 100 내지 600 kg/m3일 수 있다.When the content of the residual alkaline earth metal element per unit area of the foam sheet is in the range of 0.2 to 2.0% by weight, 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 .
상기 발포시트의 평균 두께는 1.0 내지 5.0 mm 범위일 수 있다. 예를 들어, 상기 발포시트의 평균 두께는 1.0 내지 4.0 mm, 1.0 내지 3.5 mm, 1.0 내지 3.0 mm, 1.0 내지 5.5 mm, 1.0 내지 2.0 mm, 1.0 내지 1.5 mm, 1.5 내지 5.0 mm, 2.0 내지 5.0 mm, 3.0 내지 5.0 mm, 또는 4.0 내지 5.0 mm일 수 있다.The average thickness of the foam sheet may be in the range of 1.0 to 5.0 mm. For example, 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.
본 발명에 따른 발포시트는 알칼리토금속 탄산염을 포함함으로써, 발포시트 내에 분산된 알칼리토금속 탄산염에 의해 발포시트의 셀의 사이즈는 줄이고, 밀도는 높일 수 있으며, 전체적으로 일정한 크기의 셀을 형성하며 발포 수 있도록 함으로써, 두께 편차가 7 내지 22% 범위로 일정한 두께를 갖는 발포시트를 제공할 수 있으며, 우수한 가공성을 나타낼 수 있다. 구체적으로, 상기 알칼리토금속 탄산염은 무기입자로, 알칼리토금속 탄산염을 포함함으로써 시트표면이 균일하며 우수한 열 성형성을 나타낼 수 있다.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. By doing so, it is possible to provide a foam sheet having a constant thickness in the range of 7 to 22% of the thickness deviation, and can exhibit excellent processability. Specifically, 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.
예를 들어, 상기 발포시트가 알칼리토금속 탄산염 중 탄산칼슘을 포함할 경우, 탄산칼슘의 열전도율은 1.0 내지 3.0 kcal/mh℃일 수 있으므로, 상기와 같이 탄산칼슘을 포함하는 발포시트는 우수한 열전도율을 나타냄으로써 균일한 표면을 가지고, 우수한 열 성형성을 나타낼 수 있다. 예를 들어, 상기 탄산칼슘의 열전도율은 1.2 내지 2.5 kcal/mh℃, 1.5 내지 2.2 kcal/mh℃ 또는 1.8 내지 2.0 kcal/mh℃일 수 있다. 보다 구체적으로, 탄산칼슘의 열전도율은 1.5 내지 2.5 kcal/mh℃ 또는 1.8 내지 2.3 kcal/mh℃일 수 있다. For example, when the foam sheet contains calcium carbonate among alkaline earth metal carbonates, 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. For example, 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.
상기 알칼리토금속 원소는 Ca, Mg, 및 Ba으로 이루어진 군으로부터 선택되는 1종 이상의 양이온을 포함하는 무기탄산염일 수 있다. 구체적으로, 상기 알칼리토금속 탄산염을 함유하는 무기입자는 탄산칼슘(CaCO3), 탄산마그네슘(MgCO3), 및 탄산바륨(BaCO3)을 포함할 수 있고, 보다 구체적으로, 본 발명의 무기입자는 탄산칼슘을 포함할 수 있다.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. Specifically, 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.
상기 발포시트의 단위 면적 당 무기입자의 함량, 즉 발포시트의 단위 면적 당 알칼리토금속 탄산염의 함량은 발포시트의 단위 면적 당 잔류 알칼리토금속 원소 함량을 측정함으로써 알 수 있다. 발포시트의 제조 시 폴리에스테르 수지에 알칼리토금속 탄산염을 함유하는 무기입자의 투입량 대비 발포시트의 제조 후 발포시트 내의 잔류하는 알칼리토금속 원소의 함량은 70 내지 95%일 수 있다. 예를 들어, 상기 발포시트 제조 전 투입량 대비 잔류 알칼리토금속 원소의 함량은 70 내지 90%, 70 내지 85%, 70 내지 80%, 75 내지 95%, 80 내지 95%, 85 내지 95%, 또는 90 내지 95%일 수 있다.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. In the manufacture 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%. For example, 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%.
상기 무기입자의 평균 크기는 1.0 내지 5.0 μm일 수 있다. 예를 들어, 상기 무기탄산염의 평균 입자크기는 1.0 내지 4.0 μm, 1.0 내지 3.0 μm, 1.0 내지 2.0 μm, 2.0 내지 5.0 μm, 또는 3.0 내지 5.0 μm일 수 있다.The average size of the inorganic particles may be 1.0 to 5.0 μm. For example, the average particle size of the inorganic carbonate may be 1.0 to 4.0 μm, 1.0 to 3.0 μm, 1.0 to 2.0 μm, 2.0 to 5.0 μm, or 3.0 to 5.0 μm.
본 발명에서 사용 가능한 폴리에스테르의 종류를 예를 들면, 폴리에틸렌 테레프탈레이트(Polyethylene Terephthalate, PET), 폴리부틸렌 테레프탈레이트(Polybutylene Terephthalate, PBT), 폴리락트산(Poly Lactic acid, PLA), 폴리글리코르 산(Polyglycolic acid, PGA), 폴리프로필렌(Polypropylene, PP), 폴리에틸렌(Polyethylene, PE), 폴리에틸렌 아디파트(Polyehtylene adipate, PEA), 폴리하이드로시알카노에이트(Polyhydroxyalkanoate, PHA), 폴리트리메틸렌 테레프탈레이트(Polytrimethylene Terephthalate, PTT) 및 폴리에틸렌 나프탈렌(Polyethylene naphthalate, PEN)으로 이루어진 군으로부터 선택된 하나 이상일 수 있다. Examples of the types of polyesters that can be used in the present invention include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polylactic acid (PLA), and polyglycolic acid. (Polyglycolic acid, PGA), polypropylene (PP), polyethylene (PE), polyethylene adipate (PEA), polyhydroxyalkanoate (PHA), polytrimethylene terephthalate (Polytrimethylene) It may be at least one selected from the group consisting of terephthalate, PTT) and polyethylene naphthalate (PEN).
구체적으로, 본 발명에서 폴리에스테르 발포시트는 폴리에틸렌 테레프탈레이트(Polyethylene Terephthalate, PET) 발포시트일 수 있다.Specifically, in the present invention, the polyester foam sheet may be a polyethylene terephthalate (PET) foam sheet.
상기 발포시트의 '주름(corrugation)'은 발포시트의 표면에 울퉁불퉁하거나 물결 모양으로 주름이 잡히는 것을 의미하는 것이다.The'corrugation' of the foam sheet means that the surface of the foam sheet is wrinkled in a rough or wavy shape.
상기 발포시트의 주름은 발포시트의 표면을 육안으로 확인하여 개수를 측정할 수 있으며, 발포시트의 단위 면적(가로 1 m × 세로 1 m) 당 10 개 이하일 수 있다. 예를 들어, 상기 주름은 발포시트의 단위 면적(가로 1 m × 세로 1 m) 당 0(주름 없음) 내지 10 개, 0 내지 8 개, 0 내지 6 개, 0 내지 4 개, 또는 0 내지 2 개일 수 있다.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. For example, 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.
상기 발포시트는, 표면 균일도에 대한 신뢰성 평가 시 단위 면적에서 평가등급이 2 등급 이하일 수 있다. 예를 들어, 상기 표면 균일도에 대한 신뢰성 평가는, 발포시트를 가로 1 m × 세로 1 m로 재단하고, 재단된 시트 상에 존재하는 주름의 개수를 측정할 수 있으며, 카운트된 주름의 개수를 하기의 기준에 따라 분류하여 등급을 평가한 것일 수 있다(1 등급: 주름의 개수가 0개인 경우 / 2 등급: 주름의 개수가 0개 초과 2개 이하인 경우 / 3 등급: 주름의 개수가 2개 초과 4개 이하인 경우 / 4 등급: 주름의 개수가 4개 초과 10개 이하인 경우 / 5 등급: 주름의 개수가 10개 초과인 경우). 예를 들어, 상기 발포시트는 단위 면적에서 주름의 개수가 2개 이하일 수 있다.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). For example, the foam sheet may have two or less wrinkles in a unit area.
본 발명에 따른 발포시트는 무기입자로 알칼리토금속 탄산염을 포함함으로써, 발포시트의 셀의 사이즈는 줄이고, 밀도는 높일 수 있으며, 시트표면이 균일하여 주름(corrugation)의 발생을 감소시킬 수 있다.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.
상기 발포시트는, 가로 1 cm × 세로 1 cm의 발포시트에 대한 휨(curl) 평가 시 하기 수학식 1을 만족하는 것일 수 있다: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:
[수학식 1][Equation 1]
│Lchord-0.5 mm│≤0.1 mm│L chord -0.5 mm│≤0.1 mm
수학식 1에서, Lchord은 발포시트 상에 존재하는 임의의 지점 A와 상기 지점 A로부터 0.5 mm 떨어진 지점 B의 최단 거리, 구체적으로는 지점 A와 지점 B의 "현(chord)" 길이를 나타내며, 발포시트의 휨 정도에 따라 발포시트 상에 존재하는 임의의 지점 A와 상기 지점 A로부터 0.5 mm 떨어진 지점 B(Lchord)의 거리가 0.5 mm 보다 줄어들 수 있으나, 본 발명에 따른 발포시트는 5 mm 발포시트 기준으로 줄어든 거리가 0.1 mm 이하일 수 있다.In Equation 1, 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. , Depending on the degree of bending of the foam sheet, 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.
예를 들어, 본 발명에 따른 발포시트의 휨 평가에 따른 휨 정도는 0.1 mm 이하, 예를 들어, 0(휨 발생 없음) 내지 0.1 mm, 0 내지 0.08 mm, 0 내지 0.05 mm, 0 내지 0.03 mm, 0.03 내지 0.1 mm, 또는 0.05 내지 0.1 mm일 수 있다.For example, 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.
상기 발포시트의 '휨(curl)'은 발포시트 자체가 구부러지는 것을 의미하는 것이고, 발포시트의 '주름(corrugation)'은 발포시트의 표면에 울퉁불퉁하거나 물결 모양으로 주름이 잡히는 것을 의미하는 것이다.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.
본 발명에 따른 발포시트는 무기입자로 알칼리토금속 탄산염을 포함함으로써, 발포시트의 셀의 사이즈는 줄이고, 밀도는 높일 수 있으며, 시트표면이 균일하여 주름(corrugation)의 발생을 감소시킬 수 있다.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.
또한, 본 발명은 또한, 본 발명은 일실시예에서, 폴리에스테르 수지 및 알킬리토금속 탄산염을 함유하는 무기입자를 포함하는 수지 용융물을 압출기로 압출 발포하며 발포시트를 제조하는 단계를 포함하고, 발포된 발포시트는 발포된 발포시트는 단위 면적(가로 1 m × 세로 1 m) 당 잔류 알칼리토금속 원소의 함량이 0.2 내지 2 중량% 범위이며, 하기 수학식 1을 만족하는 발포시트의 제조방법을 제공한다:In addition, 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:
[수학식 1][Equation 1]
y=a(x-b)2+7.3691y=a(xb) 2 +7.3691
수학식 1에서,In Equation 1,
y는 발포시트의 두께 편차율을 나타내고, 단위는 %이며,y represents the thickness deviation rate of the foam sheet, the unit is %,
x는 발포시트의 단위 면적당 알칼리토금속 원소의 함량을 나타내고, 단위는 중량%이며,x represents the content of alkaline earth metal elements per unit area of the foam sheet, and the unit is% by weight,
a는 6.4≤a≤7.4이고, b는 0.59≤b≤0.7이다.a is 6.4≤a≤7.4, and b is 0.59≤b≤0.7.
예를 들어, 상기 a는 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, 또는 6.6≤a≤7.0일 수 있고, b는 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, 또는 0.60≤b≤0.65일 수 있다.For example, 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 And 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.
본 발명에 따른 발포시트의 두께 편차율은 7 내지 22%일 수 있다. 예를 들어, 상기 발포시트의 두께 편차율은 7 내지 20%, 7 내지 15%, 7 내지 12%, 7 내지 10%, 10 내지 22%, 10 내지 15%, 12 내지 22%, 또는 15 내지 22%일 수 있다.The thickness deviation rate of the foam sheet according to the present invention may be 7 to 22%. For example, 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%.
상기 발포시트의 단위 면적(가로 1 m × 세로 1 m) 당 잔류 알칼리토금속 원소의 함량은 0.2 내지 2.0 중량%일 수 있다. 예를 들어, 상기 발포시트의 단위 면적 당 잔류 알칼리토금속 원소의 함량은 0.2 내지 1.8 중량%, 0.2 내지 1.6 중량%, 0.2 내지 1.4 중량%, 0.2 내지 1.2 중량%, 0.2 내지 1.0 중량%, 0.2 내지 0.5 중량%, 0.5 내지 2.0 중량%, 1.0 내지 2.0 중량%, 1.2 내지 2.0 중량%, 또는 1.5 내지 2.0 중량%일 수 있다.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. For example, 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.
상기 발포시트의 KS M ISO 845:2012에 따른 평균 발포 밀도는 100 내지 600 kg/m3일 수 있다. 예를 들어, 상기 발포시트의 평균 발포 밀도는 100 내지 500 kg/m3, 100 내지 400 kg/m3, 100 내지 300 kg/m3, 100 내지 200 kg/m3, 200 내지 600 kg/m3, 300 내지 600 kg/m3, 400 내지 600 kg/m3, 또는 500 내지 600 kg/m3일 수 있다.The foam sheet may have an average foam density of 100 to 600 kg/m 3 according to KS M ISO 845:2012. For example, 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 .
상기 발포시트의 단위 면적 당 잔류 알칼리토금속 원소의 함량이 0.2 내지 2.0 중량% 범위일 때, 발포시트에 주름(corrugation)이 발생하지 않아 시트표면이 균일할 수 있으며, 이 때의 발포시트의 KS M ISO 845:2012에 따른 평균 발포 밀도가 100 내지 600 kg/m3일 수 있다.When the content of the residual alkaline earth metal element per unit area of the foam sheet is in the range of 0.2 to 2.0% by weight, 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 .
본 발명에 따른 발포시트의 제조방법은 압출기에 도입된 폴리에스테르 수지 및 탄산칼슘을 압출기에 투입하고 용융하여 압출 발포하여 발포시트를 제조할 수 있다. 구체적으로, 폴리에스테르 수지칩 및 탄산칼슘을 혼합한 혼합물을 용융하여 압출 발포할 수 있다. 예를 들어, 폴리에스테르 수지 및 탄산칼슘을 용융하는 과정은 260 내지 300℃의 온도에서 수행될 수 있다.In the method of manufacturing a foam sheet according to the present invention, the polyester resin and calcium carbonate introduced into the extruder may be added to the extruder, melted, and extruded to form a foam sheet. Specifically, a mixture of polyester resin chips and calcium carbonate may be melted to perform extrusion foaming. For example, the process of melting the polyester resin and calcium carbonate may be performed at a temperature of 260 to 300°C.
하나의 예시에서, 상기 알칼리토금속 탄산염을 함유하는 무기입자는 마스터배치 형태로 폴리에스테르 수지와 혼합되어 수지 용융물을 제조할 수 있다. In one example, 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.
또한, 하나의 예시에서, 폴리에스테르 수지를 압출기에 도입하는 단계는 폴리에스테르 수지는 펠렛(pellet), 그래뉼(granule), 비드(bead), 칩(chip) 등의 형태를 가질 수 있으며, 경우에 따라서는 분말(powder) 형태로 압출기에 도입될 수 있다. In addition, in one example, in the step of introducing the polyester resin into the extruder, the polyester resin may have a shape such as a pellet, granule, bead, chip, etc. Thus, it can be introduced into the extruder in powder form.
상기 압출 발포된 발포시트의 온도는 220 내지 270℃의 범위일 수 있다. 상기 압출 발포된 발포시트의 온도는 발포장치를 이용하여 수지 용융물 발포시트로 압출 발포할 때 발포장치의 압출 다이(die)와 맨드럴(nadrel) 사이에 압출 발포된 발포시트의 온도를 의미하는 것일 수 있다. 예를 들어, 상기 압출 발포된 발포시트의 온도는 220 내지 250℃, 220 내지 230℃, 230 내지 270℃, 또는 250 내지 270℃일 수 있다.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. For example, 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.
상기와 같이 알칼리토금속 탄산염을 알칼리토금속 탄산염을 포함함으로써, 발포시트의 셀의 사이즈는 줄이고, 밀도는 높일 수 있으며, 시트표면이 균일하여 주름(corrugation)의 발생을 감소시킬 수 있으며, 우수한 열 성형성을 나타낼 수 있다. 또한, 폴리에스테르 수지 내에 탄산칼슘이 균일하게 분포하여 상기 수지를 압출 발포한 발포시트는 열 전도율이 높아져 발포시트 성형시에 발포시트가 찢어지는 문제를 해결할 수 있다.By including the alkaline earth metal carbonate as described above, 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. In addition, since calcium carbonate is uniformly distributed in the polyester resin, 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.
상기 알칼리토금속 원소는 Ca, Mg, 및 Ba으로 이루어진 군으로부터 선택되는 1종 이상의 양이온을 포함하는 무기탄산염일 수 있다. 구체적으로, 상기 알칼리토금속 탄산염을 함유하는 무기입자는 탄산칼슘(CaCO3), 탄산마그네슘(MgCO3), 및 탄산바륨(BaCO3)을 포함할 수 있고, 보다 구체적으로, 본 발명의 무기입자는 탄산칼슘을 포함할 수 있다.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. Specifically, 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.
상기 발포시트의 단위 면적 당 무기입자의 함량, 즉 발포시트의 단위 면적 당 알칼리토금속 탄산염의 함량은 발포시트의 단위 면적 당 잔류 알칼리토금속 원소 함량을 측정함으로써 알 수 있다.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.
발포시트의 제조 시 폴리에스테르 수지에 알칼리토금속 탄산염을 함유하는 무기입자의 투입량 대비 발포시트의 제조 후 발포시트 내의 잔류하는 알칼리토금속 원소의 함량은 70 내지 95%일 수 있다. 예를 들어, 상기 발포시트 제조 전 투입량 대비 잔류 알칼리토금속 원소의 함량은 70 내지 90%, 70 내지 85%, 70 내지 80%, 70 내지 85%, 70 내지 80%, 75 내지 95%, 80 내지 95%, 85 내지 95%, 또는 90 내지 95%일 수 있다.In the manufacture 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%. For example, 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%.
상기 무기입자의 평균 크기는 1.0 내지 5.0 μm일 수 있다. 예를 들어, 상기 무기탄산염의 평균 입자크기는 1.0 내지 4.0 μm, 1.0 내지 3.0 μm, 1.0 내지 2.0 μm, 2.0 내지 5.0 μm, 또는 3.0 내지 5.0 μm일 수 있다.The average size of the inorganic particles may be 1.0 to 5.0 μm. For example, the average particle size of the inorganic carbonate may be 1.0 to 4.0 μm, 1.0 to 3.0 μm, 1.0 to 2.0 μm, 2.0 to 5.0 μm, or 3.0 to 5.0 μm.
상기 발포시트의 단위 면적 당 잔류 무기탄산염 함량을 측정하는 방법은, 발포시트를 산성 용매에서 전처리한 후 원자흡광광도계로 양이온 분석을 통해 측정하는 것일 수 있다.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.
본 발명에 따른 발포시트의 제조방법은 평균 15% 이하의 두께 편차를 나타내는 발포시트를 제조할 수 있다. 구체적으로, 본 발명에 따른 발포시트의 제조방법은 평균 12% 이하, 10% 이하, 8% 이하, 7% 이하, 또는 5% 이하의 두께편차를 나타내는 발포시트를 제조할 수 있다. 보다 구체적으로, 본 발명에 따른 발포시트의 제조방법은 평균 1 내지 10% 또는 5 내지 8%의 두께편차를 나타내는 발포시트를 제조할 수 있다.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%.
본 발명에 따른 폴리에스테르 발포시트의 제조방법은, 폴리에스테르 발포시트를 열처리하여 후발포 하는 공정을 수행함으로써, 폴리에스테르 발포시트를 활용한 작업 시 열을 가했을 때 부피변화율이 낮아 후발포되는 현상을 방지할 수 있고, 후발포에 의해 폴리에스테르 발포시트의 두께가 두꺼워짐에 따라 결정화도가 높아지며, 굴곡강도가 높아질 수 있다.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.
상기 압출 발포된 폴리에스테르 발포시트의 열처리 단계에서, 열처리함에 따른 발포시트의 표면 온도와 열처리 시간은 폴리에스테르 발포시트의 두께에 영향을 줄 수 있고, 본 발명에 따른 열처리 온도와 시간 범위에서 열처리함으로써 폴리에스테르 발포시트의 결정화도, 내열성 및 굴곡강도를 향상시킬 수 있다.In the heat treatment step of the extruded foamed polyester foam sheet, 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.
상기 압출 발포된 폴리에스테르 발포시트를 열처리하는 단계는, 30 내지 200 초 동안 열처리 하는 것일 수 있고, 예를 들어, 상기 열처리는 30 내지 200 초, 30 내지 150 초, 30 내지 100 초, 30 내지 50 초, 50 내지 200 초, 100 내지 200 초, 또는 150 내지 200 초 동안 수행하는 것일 수 있다. 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.
상기 압출 발포된 폴리에스테르 발포시트를 열처리하는 단계는, 열처리에 의해 표면 온도가 120 내지 250℃인 폴리에스테르 발포시트를 제조하는 것일 수 있고, 예를 들어, 상기 표면 온도는 120 내지 250℃, 120 내지 230℃, 120 내지 200℃, 120 내지 180℃, 120 내지 160℃, 120 내지 140℃, 140 내지 250℃, 160 내지 250℃, 180 내지 250℃, 200 내지 250℃, 또는 230 내지 250℃일 수 있다.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.
상기 압출 발포된 폴리에스테르 발포시트를 열처리하는 단계는 직접 열처리 및 간접 열처리 방법을 포함할 수 있고, 예를 들어, 직접 열처리는 발포시트의 표면에 직접적으로 열을 가하는 것일 수 있고, 간접 열처리는 열처리 분위기의 온도를 조절하여 열을 가하는 것일 수 있다. 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.
상기 직접 열처리는, 압출 발포된 폴리에스테르 발포시트의 표면 온도를 120 내지 300℃ 온도로 가열하는 것일 수 있다. 예를 들어, 압출 발포된 폴리에스테르 발포시트의 표면 온도를 120 내지 300℃, 120 내지 200℃, 120 내지 150℃, 150 내지 300℃, 또는 200 내지 300℃ 온도로 가열하는 것일 수 있다.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. For example, 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.
상기 압출 발포된 폴리에스테르 발포시트의 일면 또는 양면에 접촉시켜 열처리하여 압출 발포된 폴리에스테르 발포시트의 표면 온도를 120 내지 300℃ 온도로 가열하는 것일 수 있고, 상기 폴리에스테르 발포시트의 일면 또는 양면을 가열하는 히팅 플레이트 온도는 100 내지 300℃, 100 내지 250℃, 100 내지 200℃, 100 내지 150℃, 150 내지 300℃, 200 내지 300℃, 250 내지 300℃ 범위일 수 있다.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.
상기 간접 열처리는, 압출 발포된 폴리에스테르 발포시트를 열처리하는 단계는, 120 내지 600℃ 분위기에서 열처리하는 것일 수 있다. 예를 들어, 상기 압출 발포된 폴리에스테르 발포시트를 120 내지 600℃, 120 내지 400℃, 120 내지 200℃, 150 내지 600℃, 200 내지 600℃, 또는 400 내지 600℃ 분위기에서 열처리하여 압출 발포된 폴리에스테르 발포시트의 표면 온도를 120 내지 300℃ 온도로 가열하는 것일 수 있다. In the indirect heat treatment, the heat treatment of the extruded foamed polyester foam sheet may be heat treatment in an atmosphere of 120 to 600°C. For example, 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 ℃.
본 발명에 따른 압출 발포된 폴리에스테르 발포시트의 열처리 수행 시 열처리 온도가 상기 범위일 경우 압출 발포된 폴리에스테르 발포시트가 1.5 내지 3 배로 후발포하는데 용이할 수 있다.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.
상기 압출 발포된 폴리에스테르 발포시트의 열처리 후 발포배율은 열처리 전 발포배율의 1.5 내지 3 배일 수 있다. 상기 열처리는 압출 발포된 폴리에스테르 발포시트의 후발포를 수행하는 것일 수 있고, 후발포(열처리) 전 발포배율보다 1.5 내지 3 배 더 발포될 수 있다. After the heat treatment of the extruded foamed polyester foam sheet, 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).
상기 폴리에스테르 발포시트의 평균 두께는 1.5 내지 10 mm일 수 있다. 상기 폴리에스테르 발포시트의 평균 두께는 압출 발포된 폴리에스테르 발포시트의 열처리 전보다 1.5 내지 2 배 증가한 것일 수 있고, 예를 들어, 상기 폴리에스테르 발포시트의 평균 두께는 1.5 내지 10 mm, 1.5 내지 8 mm, 1.5 내지 5 mm, 5 내지 10 mm, 또는 7.5 내지 10 mm일 수 있다.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.
상기 압출 발포된 폴리에스테르 발포시트를 열처리하는 단계를 거침으로써 폴리에스테르 발포시트의 발포 배율을 높이게 되며, 이에 따라 제조된 폴리에스테르 발포시트에 열을 가할 시 후발포가 발생하여 형태가 변형되는 것을 방지할 수 있다.By passing through the step of heat treatment of the extruded foamed polyester foam sheet, 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.
예를 들어, 압축 발포된 폴리에스테르 발포시트는 컨베이어 벨트에 의해 히터를 지나면서 가열되어 열처리(후발포)될 수 있고, 압축 발포된 폴리에스테르 발포시트는 전단부와 후단부를 평행하게 잡아주는 닙롤러(Nip Roller)에 의해서 히터를 지나면서 가열되어 열처리(후발포)될 수 있다.For example, 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).
압축 발포된 폴리에스테르 발포시트의 열처리 이후, 폴리에스테르 발포시트를 냉각하는 단계를 더 거칠 수 있다. 상기 냉각하는 단계는 폴리에스테르 발포시트가 컨베이어 벨트에 의해 이동하면서 냉각 롤러에 의해 냉각될 수 있다. 이때, 냉각하는 단계는 폴리에스테르 발포시트가 열처리에 의해 용융되어있던 부분을 굳혀, 상기 폴리에스테르 발포시트의 형태가 뒤틀리 현상을 방지하기 위해 수행될 수 있다. After the heat treatment of the compression foamed polyester foam sheet, 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. In this case, 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.
하나의 예로서, 상기 냉각하는 단계에서 냉각 롤러의 온도는 15℃ 이하, 1 내지 14.5℃, 1.5 내지 14℃, 2 내지 13.5℃¸2.5 내지 13℃, 3 내지 12.5℃, 3.5 내지 12℃, 4 내지 11.5℃ 혹은 4.5 내지 10℃ 범위일 수 있다. As an example, in the cooling step, 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.
압축 발포된 폴리에스테르 발포시트의 열처리 이후, 폴리에스테르 발포시트를 일정 간격으로 컷팅하는 단계를 더 거칠 수 있다. 상기 컷팅하는 단계는 폴리에스테르 발포시트가 컨베이어 벨트에 의해 이동하면서 커터에 의해 컷팅될 수 있다.After the heat treatment of the compression foamed polyester foam sheet, 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.
또한, 상기 컷팅하는 단계는 압축 발포된 폴리에스테르 발포시트의 열처리 후에 폴리에스테르 발포시트가 컨베이어 벨트에 의해 이동하면서 냉각 롤러를 지나 냉각된 후 컨베이어 벨트에 의해 이동하면서 커터에 의해 커팅될 수 있다. 본 발명에 따른 폴리에스테르 발포시트는의 제조방법은 열처리된 압출 발포된 폴리에스테르 발포시트를 커터에 의해 컷팅하는 과정을 수행함으로써, 공정성이 향상되고 대량생산이 용이한 이점이 있다.In addition, in the step of cutting, after heat treatment of the compressed foamed polyester foam sheet, 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.
하나의 예로서, 본 발명에 따른 발포시트를 제조하는 단계는, 다양한 형태의 첨가제가 투입될 수 있다. 상기 첨가제는 필요에 따라, 유체 연결 라인 중에 투입되거나, 혹은 발포 공정 중에 투입될 수 있다. 첨가제의 예로는, 배리어(Barrier) 성능, 친수화 기능 또는 방수 기능을 가질 수 있으며, 증점제, 계면활성제, 친수화제, 열안정제, 방수제, 셀 크기 확대제, 적외선 감쇠제, 가소제, 방화화학 약품, 안료, 탄성폴리머, 압출 보조제, 산화방지제, 기핵제, 공전 방지제 및 UV 흡수제로 이루어진 군으로부터 선택되는 하나 이상의 기능성 첨가제를 포함할 수 있다. 구체적으로, 본 발명의 발포시트 제조방법은 증점제, 기핵제, 열안정제 및 발포제 중 1종 이상을 투입할 수 있으며, 앞서 열거된 기능성 첨가제들 중 1종 이상을 더 포함할 수 있다.As an example, in the step of preparing the foam sheet according to the present invention, various types of additives may be added. If necessary, the additive may be introduced into the fluid connection line or added during the foaming process. Examples of 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. Specifically, 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.
예를 들어, 본 발명의 발포시트를 제조하는 단계는 증점제, 친수화제, 열안정제, 방수제, 셀 크기 확대제, 적외선 감쇠제, 가소제, 방화 화학 약품, 안료, 탄성폴리머, 압출 보조제, 산화방지제, 공전 방지제 및 UV 흡수제로 이루어진 군으로부터 선택되는 하나 이상의 첨가제를 유체 연결 라인 중에 투입할 수 있다. 발포시트 제조시 필요한 첨가제 중에서, 유체 연결 라인 중에 투입되지 않은 첨가제는, 압출 공정 중에 투입 가능하다.For example, 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. Among the additives required for manufacturing the foam sheet, additives not added to the fluid connection line may be added during the extrusion process.
상기 증점제는 특별히 한정하지 않으나, 본 발명에서는 예를 들면 피로멜리트산 이무수물(PMDA)가 사용될 수 있다.The thickener is not particularly limited, but in the present invention, for example, pyromellitic dianhydride (PMDA) may be used.
상기 열안정제는, 유기 또는 무기인 화합물일 수 있다. 상기 유기 또는 무기인 화합물은, 예를 들어, 인산 및 그 유기 에스테르, 아인산 및 그 유기 에스테르일 수 있다. 예를 들어, 상기 열안정제는 상업적으로 입수 가능한 물질로서, 인산, 알킬 포스페이트 또는 아릴 포스페이트일 수 있다. 구체적으로, 본 발명에서 열안정제는 트리페닐 포스페이트일 수 있으나, 이에 제한되는 것은 아니며, 상기 수지 발포시트의 열적 안정성을 향상시킬 수 있는 것이라면, 통상적인 범위 내에서 제한 없이 사용 가능하다.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. For example, the heat stabilizer is a commercially available material, and may be phosphoric acid, alkyl phosphate or aryl phosphate. Specifically, in the present invention, 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.
상기 발포제의 예로는, N2, CO2, 프레온, 부탄, 펜탄, 네오펜탄, 헥산, 이소헥산, 헵탄, 이소헵탄, 메틸클로라이드 등의 물리적 발포제를 사용할 수 있으며, 구체적으로 본 발명에서는 부탄이 사용될 수 있다.As an example of the blowing agent, a physical blowing agent such as N 2 , CO 2 , freon, butane, pentane, neopentane, hexane, isohexane, heptane, isoheptane, methyl chloride, etc. can be used, and specifically butane is used in the present invention. I can.
또한, 방수제는 특별히 한정되지 않으며, 예를 들어, 실리콘 계열, 에폭시 계열, 시아노아크릴산 계열, 폴리비닐아크릴레이트 계열, 에틸렌비닐아세테이트 계열, 아크릴레이트 계열, 폴르클로로프렌 계열, 폴리우레탄 수지와 폴리에스터 수지의 혼합체 계열, 폴리올과 폴리 우레텐 수지의 혼합체 계열, 아크릴릭 폴리머와 폴리우레탄 수지의 혼합체 계열, 폴리이미드 계열 및 시아노아크릴레이트와 우레탄의 혼합체 계열 등의 혼합물을 포함할 수 있다.In addition, 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.
아울러, 본 발명은 상기 발포시트를 포함하는 식품용기를 제공한다. 본 발명에 따른 식품용기는 무기입자로 무기탄산염을 포함함으로써 식품용기의 표면이 균일하며 제조시 불량률이 낮을 수 있다.In addition, 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.
이하 본 발명에 따르는 실시예 등을 통해 본 발명을 보다 상세히 설명하나, 본 발명의 범위가 하기 제시된 실시예에 의해 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples according to the present invention, but the scope of the present invention is not limited by the examples presented below.
실시예 1Example 1
폴리에스테르 발포시트를 제조하기 위해, 먼저 폴리에틸렌 테레프탈레이트(PET) 수지 100 중량부를 180℃에서 건조하여 수분을 제거하였고, 압출기에 상기 수분이 제거된 PET 수지와 상기 수분이 제거된 PET 수지 100 중량부를 기준으로, 평균 입자사이즈 1.0 내지 5.0 μm의 탄산칼슘 3.1 중량부를 혼합하고, PET 수지 100 중량부를 기준으로, 피로멜리틱 디언하이드리드 0.5중량부 및 Irganox (IRG 1010) 0.1 중량부를 혼합하고, 280℃로 가열하여 수지 용융물을 제조하였다. 그런 다음, 제1 압출기에 발포제로서 부탄을 PET 수지 100 중량부를 기준으로 1.5 중량부 투입하고 압출발포 하였으며, 평균 2.0 mm 두께의 PET 발포시트를 제조하였다. 이때, 제조된 PET 발포시트의 밀도는 350 kg/m3 였다.In order to manufacture a polyester foam sheet, 100 parts by weight of a polyethylene terephthalate (PET) resin was first dried at 180° C. to remove moisture, and the PET resin from which the moisture was removed and the PET resin from which the moisture was removed 100 parts by weight in an extruder As a standard, 3.1 parts by weight of calcium carbonate having an average particle size of 1.0 to 5.0 μm are mixed, 0.5 parts by weight of pyromellitic dianhydride and 0.1 parts by weight of Irganox (IRG 1010) are mixed, based on 100 parts by weight of PET resin, and 280°C By heating to prepare a resin melt. Then, 1.5 parts by weight of butane was added to the first extruder as a foaming agent based on 100 parts by weight of the PET resin, followed by extrusion foaming, and a PET foam sheet having an average thickness of 2.0 mm was prepared. At this time, the density of the prepared PET foam sheet was 350 kg/m 3 .
실시예 2Example 2
탄산칼슘 1.9 중량부를 혼합한 것을 제외하고는, 실시예 1과 동일한 방법으로 평균 1.0 mm 두께의 PET 발포시트를 제조하였으며, 제조된 PET 발포시트의 밀도는 280 kg/m3 였다.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 .
실시예 3Example 3
탄산칼슘 1.7 중량부를 혼합한 것을 제외하고는, 실시예 1과 동일한 방법으로 평균 2.2 mm 두께의 PET 발포시트를 제조하였으며, 제조된 PET 발포시트의 밀도는 240 kg/m3 였다.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 .
실시예 4Example 4
탄산칼슘 1.5 중량부를 혼합한 것을 제외하고는, 실시예 1과 동일한 방법으로 평균 2.0 mm 두께의 PET 발포시트를 제조하였으며, 제조된 PET 발포시트의 밀도는 200 kg/m3 였다.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 .
비교예 1Comparative Example 1
탄산칼슘 5.5 중량부를 혼합한 것을 제외하고는, 실시예 1과 동일한 방법으로 평균 2.0 mm 두께의 PET 발포시트를 제조하였으며, 제조된 PET 발포시트의 밀도는 350 kg/m3 였다.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 .
비교예 2Comparative Example 2
탄산칼슘 0.4 중량부를 혼합한 것을 제외하고는, 실시예 1과 동일한 방법으로 평균 2.0 mm 두께의 PET 발포시트를 제조하였으며, 제조된 PET 발포시트의 밀도는 200 kg/m3 였다.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 .
실험예: 발포시트의 물성 평가Experimental Example: Evaluation of physical properties of foam sheet
본 발명에 따른 발포시트의 물성을 평가하기 위하여, 실시예 및 비교예에서 제조된 발포시트를 대상으로 하기와 같은 실험을 수행하였다.In order to evaluate the physical properties of the foam sheet according to the present invention, the following experiment was performed on the foam sheets prepared in Examples and Comparative Examples.
가) 시트 내 알칼리토금속 원소 함량 평가A) Evaluation of the content of alkaline earth metal elements in the sheet
각 발포시트를 800℃ 전기로에 넣고 3 시간 동안 회화한 후, 남은 잔량을 산성 용매로 전처리한 후 원자흡광광도계(atomic absorption spectrometer, AAS)로 측정하였다. 구체적으로, 상기 전처리는 회화된 시료를 36% 염산 3 mL 및 60% 질산 1 mL로 용해하고, 3 μm 여과지로 여과하여 100 mL 플라스크에 취한 후 표선까지 증류수로 채워 수행하였다. 상기 용액을 원자흡광광도계(Varian社, SpectrAA-30)를 이용하여 Ca 원소 함량을 측정하였고, 측정값은 검량선을 통해 수득하였다. 검량선은 Ca 표준액 (Kanto Chemical社, Ca 1,000 ppm)을 사용하여 수득하였다.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 μm 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).
나) 발포시트의 평균 두께 및 발포밀도 평가B) Evaluation of average thickness and foam density of foam sheet
각 발포시트의 평균 두께를 측정하기 위하여 각 발포시트의 전폭을 일정한 간격으로 8분할하여 인디게이터를 이용하여 두께를 측정한 후(ID-C112, MItutoyo社), 평균값을 계산하였다.In order to measure the average thickness of each foam sheet, 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.
또한, 각 발포시트의 평균 발포밀도를 측정하기 위하여 각 발포시트를 가로 2 ㎝ × 세로 2 ㎝로 샘플을 취한 후 수중식 전자밀도계(EW300SG, MIRAGE社) 로 발포밀도를 측정하였다.In addition, in order to measure the average foam density of each foam sheet, after taking a sample of each foam sheet in a width of 2 cm × 2 cm in length, the foam density was measured with an underwater electronic density meter (EW300SG, MIRAGE).
발포시트의 두께 편차를 나타내는 상기 수학식 1은 실시예 1 내지 4 및 비교예 1의 측정된 값을 이용하여 도출하였고, 이에 대한 그래프는 도 1에 나타내었다. 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.
다) 발포시트의 신뢰성 평가C) Reliability evaluation of foam sheet
각 발포시트의 신뢰성, 구체적으로는 압출발포된 시트의 형상 균일도를 평가하였다.The reliability of each foam sheet, specifically, the shape uniformity of the extruded foam sheet was evaluated.
다-1) 주름 개수 측정C-1) Wrinkle count measurement
각 발포시트를 가로 1 m × 세로 1 m로 재단하고, 재단된 시트 상에 존재하는 주름의 개수를 카운트하였으며, 카운트된 주름의 개수를 하기의 기준에 따라 분류하여 등급을 평가하였다: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:
1 등급: 주름의 개수가 0개인 경우Grade 1: When the number of wrinkles is zero
2 등급: 주름의 개수가 0개 초과 2개 이하인 경우Grade 2: When the number of wrinkles exceeds 0 and 2 or less
3 등급: 주름의 개수가 2개 초과 4개 이하인 경우Grade 3: When the number of wrinkles is more than 2 and 4 or less
4 등급: 주름의 개수가 4개 초과 10개 이하인 경우Grade 4: When the number of wrinkles is more than 4 and not more than 10
5 등급: 주름의 개수가 10개 초과인 경우Grade 5: When the number of wrinkles exceeds 10
다-2) 휨정도 측정C-2) Measurement of warpage
각 발포시트를 가로 1.0 cm × 세로 1.0 cm로 재단하고, 재단된 시트를 초정밀 3차원 조면계(Ultrahigh accurate 3-D profilometer UA3P-300, Panasonic Corporation) 상에 고정시켰다. 이후, 고정된 시트 상에 존재하는 임의의 지점 A과 상기 지점 A로부터 0.5 mm 떨어진 지점 B의 최단 거리(구체적으로는 지점 A와 지점 B의 "현" 길이)를 측정하고, 하기 수학식 1을 이용하여 발포시트의 표면 균일도를 평가하였다. 이때, 측정 온도는 23℃, 상대습도는 60%였으며, 측정 시 진동 가속도는 0.5 cm/s2 였다.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 .
[수학식 1][Equation 1]
발포시트의 휨 정도 = │Lchord-0.5 mm│The degree of deflection of the foam sheet = │L chord -0.5 mm│
수학식 1에서,In Equation 1,
Lchord 은 발포시트 상에 존재하는 임의의 지점 A와 상기 지점 A로부터 0.5 mm 떨어진 지점 B의 최단 거리를 나타낸다.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.
라) 발포시트의 성형성D) Formability of foam sheet
성형성 실험은 히터(heater)의 상부를 400℃, 하부를 320℃로 가열하여 발포시트의 표면온도가 155℃ 내지 160℃(상세 온도는 하기 표 1 참고)가 되면 80℃ 온도의 금형으로 성형하여 발포시트의 성형도를 관찰하였다.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.
Figure PCTKR2019011327-appb-T000001
Figure PCTKR2019011327-appb-T000001
상기 표 1을 살펴보면, 실시예 1 내지 4의 발포시트는 두께편차가 10% 이하로 표면의 균일한 것을 알 수 있다. 반면, 비교예 1은 탄산칼슘의 투입량이 5.5 중량%로 많은 양을 함유하여 발포공정에서 시트에 주름(20 개)이 발생하고, 두께편차가 24%로 나타난 것을 확인할 수 있었다. 상기 주름은 발포시트 내에 형성된 주름을 육안으로 확인하여 개수를 측정하였다.Looking at Table 1, it can be seen that the foam sheets of Examples 1 to 4 have a uniform surface thickness of 10% or less. On the other hand, 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.
실시예 1 내지 4 및 비교예 1의 휨 정도는, 상기 수학식 1(│Lchord-0.5 mm│)에 따라 각각 0.030, 0.045, 0.015, 0.005, 및 0.02 mm로 전체적으로 휨은 거의 발생하지 않은 것으로 확인하였다.The degree of warpage of Examples 1 to 4 and Comparative Example 1 was 0.030, 0.045, 0.015, 0.005, and 0.02 mm, respectively, according to Equation 1 (│L chord -0.5 mm│). Confirmed.
또한, 비교예 2는 탄산칼슘의 투입량이 0.4 중량%로 칼슘 함량이 낮아 기핵 역할이 부족하여 발포 자체가 되지 않아, 발포시트를 제조할 수 없었다.In addition, in Comparative Example 2, the amount of calcium carbonate added was 0.4% by weight, and the calcium content was low, and thus foaming itself was not performed due to the lack of a nucleus role.
또한, 본 발명에 따른 발포시트를 성형하여 식품용기로 제조하여 성형성을 실험한 결과, 실시예 1 내지 실시예 4는 성형성이 전반적으로 양호한 것을 확인할 수 있었다. 구체적으로, 실시예 1 내지 4는 미세윤곽도 양호한 동시에 주름도 형성되지 않은 것을 확인할 수 있었다. 또한, 실시예 1 내지 4는 탄산칼슘의 영향으로 낮은 온도에서도 성형성이 양호한 것을 확인할 수 있었다. In addition, as a result of testing the moldability by molding the foam sheet according to the present invention and manufacturing it into a food container, it was confirmed that the moldability of Examples 1 to 4 was generally good. Specifically, it was confirmed that Examples 1 to 4 had good micro-contours and no wrinkles. In addition, it was confirmed that Examples 1 to 4 had good moldability even at low temperatures due to the influence of calcium carbonate.
도 2a 및 도 2b는 각각 본 발명의 비교예에 따른 주름이 발생한 발포시트(비교예) 및 본 발명의 실시예에 따른 주름이 발생하지 않은 발포시트의 사진이다. 이를 통해서, 본 발명에 따른 발포시트는 탄산칼슘을 일정 함량으로 포함함으로써, 발포시트의 제조 후에도 일정 함량의 탄산칼슘을 포함할 수 있으며, 이에 따라 발포시트 제조과정에서 주름이 형성되지 않고 발포시트의 두께가 일정하며 성형시에 성형성이 우수한 것을 알 수 있다.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. Through this, 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.
본 발명에 따른 발포시트는 폴리에스테르 수지에 알칼리토금속 탄산염을 함유하는 무기입자를 분산시킴으로써, 발포시트의 단위 면적(가로 1 m × 세로 1 m) 당 잔류 알칼리토금속 원소의 함량이 0.2 내지 2.0 중량% 범위이며, 발포시트의 두께 편차 10% 이하로 두께가 일정한 두께를 갖는 발포시트를 제공할 수 있다. In the foam sheet according to the present invention, by dispersing inorganic particles containing alkaline earth metal carbonate in a polyester resin, 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.
본 발명에 따른 발포시트는 무기입자를 포함함으로써 발포시트의 셀의 사이즈는 줄이고, 밀도는 높일 수 있으며, 시트표면이 균일하여 주름(corrugation)의 발생을 감소시킬 수 있으며, 우수한 열 성형성을 나타낼 수 있다. 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.

Claims (12)

  1. 폴리에스테르 수지에 알킬리토금속 탄산염을 함유하는 무기입자가 분산된 폴리에스테르 발포시트로서,As a polyester foam sheet in which inorganic particles containing an alkylri earth metal carbonate are dispersed in a polyester resin,
    발포시트의 단위 면적(가로 1 m × 세로 1 m) 당 잔류 알칼리토금속 원소의 함량이 0.2 내지 2 중량% 범위이며,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,
    하기 수학식 1을 만족하는 발포시트:Foam sheet satisfying the following Equation 1:
    [수학식 1][Equation 1]
    y=a(x-b)2+7.3691y=a(xb) 2 +7.3691
    수학식 1에서,In Equation 1,
    y는 발포시트의 두께 편차율을 나타내고, 단위는 %이며, y represents the thickness deviation rate of the foam sheet, the unit is %,
    x는 발포시트의 단위 면적당 알칼리토금속 원소의 함량을 나타내고, 단위는 중량%이며,x represents the content of alkaline earth metal elements per unit area of the foam sheet, and the unit is% by weight,
    a는 6.4≤a≤7.4이고, b는 0.59≤b≤0.7이다.a is 6.4≤a≤7.4, and b is 0.59≤b≤0.7.
  2. 제 1 항에 있어서,The method of claim 1,
    발포시트의 KS M ISO 845:2012에 따른 평균 발포 밀도는 100 내지 600 kg/m3인 발포시트.The foam sheet has an average foam density of 100 to 600 kg/m 3 according to KS M ISO 845:2012.
  3. 제 1 항에 있어서,The method of claim 1,
    발포시트의 평균 두께는 1.0 내지 5.0 mm 범위인 발포시트.The average thickness of the foam sheet is in the range of 1.0 to 5.0 mm foam sheet.
  4. 제 1 항에 있어서,The method of claim 1,
    알칼리토금속 원소는 Ca, Mg, 및 Ba으로 이루어진 군으로부터 선택되는 1종 이상의 양이온을 포함하는 무기탄산염인 발포시트.The alkaline earth metal element is an inorganic carbonate foam sheet containing at least one cation selected from the group consisting of Ca, Mg, and Ba.
  5. 제 1 항에 있어서,The method of claim 1,
    무기입자의 평균 크기는 1.0 내지 5.0 μm인 발포시트.Foam sheet having an average size of inorganic particles of 1.0 to 5.0 μm.
  6. 제 1 항에 있어서,The method of claim 1,
    폴리에스테르 수지는 폴리에틸렌 테레프탈레이트(Polyethylene Terephthalate, PET), 폴리부틸렌 테레프탈레이트(Polybutylene Terephthalate, PBT), 폴리트리메틸렌 테레프탈레이트(Polytrimethylene Terephthalate, PTT), 폴리에틸렌 나프탈레이트(Polyethylene naphthalate, PEN), 폴리에틸렌 아디파트(Polyehtylene adipate, PEA), 폴리락트산(Poly Lactic acid, PLA), 및 폴리글리코르산(Polyglycolic acid, PGA)으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 발포시트.Polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polyethylene addi Foam sheet comprising at least one selected from the group consisting of parts (Polyehtylene adipate, PEA), polylactic acid (PLA), and polyglycolic acid (PGA).
  7. 제 1 항에 있어서,The method of claim 1,
    발포시트는, 표면 균일도에 대한 신뢰성 평가 시 단위 면적에서 평가등급이 2 등급 이하인 발포시트.Foam sheet is a foam sheet with an evaluation grade of 2 or less in unit area when evaluating the reliability of surface uniformity.
  8. 제 1 항에 있어서,The method of claim 1,
    발포시트는, 가로 1 cm × 세로 1 cm의 발포시트에 대한 휨(curl) 평가 시 하기 수학식 1을 만족하는 발포시트:The foam sheet is a foam sheet that satisfies the following Equation 1 when evaluating the curl for a foam sheet having a width of 1 cm x 1 cm:
    [수학식 1][Equation 1]
    │Lchord-0.5 mm│≤0.1 mm│L chord -0.5 mm│≤0.1 mm
    수학식 1에서,In Equation 1,
    Lchord은 발포시트 상에 존재하는 임의의 지점 A와 상기 지점 A로부터 0.5 mm 떨어진 지점 B의 최단 거리를 나타낸다.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.
  9. 폴리에스테르 수지 및 알킬리토금속 탄산염을 함유하는 무기입자를 포함하는 수지 용융물을 압출기로 압출 발포하며 발포시트를 제조하는 단계를 포함하고,Comprising 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 produce a foam sheet,
    발포된 발포시트는 발포된 발포시트는 단위 면적(가로 1 m × 세로 1 m) 당 잔류 알칼리토금속 원소의 함량이 0.2 내지 2 중량% 범위이며,In the foamed foam sheet, the foamed foam sheet has a residual alkaline earth metal content of 0.2 to 2% by weight per unit area (1 m wide x 1 m long),
    하기 수학식 1을 만족하는 발포시트의 제조방법:A method of manufacturing a foam sheet satisfying the following Equation 1:
    [수학식 1][Equation 1]
    y=a(x-b)2+7.3691y=a(xb) 2 +7.3691
    수학식 1에서,In Equation 1,
    y는 발포시트의 두께 편차율을 나타내고, 단위는 %이며,y represents the thickness deviation rate of the foam sheet, the unit is %,
    x는 발포시트의 단위 면적당 알칼리토금속 원소의 함량을 나타내고, 단위는 중량%이며,x represents the content of alkaline earth metal elements per unit area of the foam sheet, and the unit is% by weight,
    a는 6.4≤a≤7.4이고, b는 0.59≤b≤0.7이다.a is 6.4≤a≤7.4, and b is 0.59≤b≤0.7.
  10. 제 9 항에 있어서,The method of claim 9,
    알칼리토금속 원소는 Ca, Mg, 및 Ba으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 무기탄산염인 발포시트의 제조방법.The alkaline earth metal element is an inorganic carbonate containing at least one selected from the group consisting of Ca, Mg, and Ba.
  11. 제 9 항에 있어서,The method of claim 9,
    무기입자의 평균 크기는 1 내지 5 μm인 발포시트의 제조방법.A method of manufacturing a foam sheet having an average size of inorganic particles of 1 to 5 μm.
  12. 제 9 항에 있어서,The method of claim 9,
    압출 발포된 발포시트의 온도는 220 내지 270℃인 발포시트의 제조방법.The temperature of the extruded foamed foam sheet is 220 to 270 ℃ method for producing a foam sheet.
PCT/KR2019/011327 2019-04-25 2019-09-03 Foam sheet comprising inorganic particles, and manufacturing method therefor WO2020218684A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0118112B1 (en) * 1988-12-01 1997-09-30 마쓰다 쇼헤이 Process for producing thermoplastic polyester resin foam
EP2612881A1 (en) * 2012-01-05 2013-07-10 Omya Development AG Fillers for foamed rigid polymer products
KR20150078004A (en) * 2013-12-30 2015-07-08 도레이케미칼 주식회사 Microporous thermoplastic polymer resin foam with enhanced mechanical strength and foaming rate and the preparation thereof
KR20150099390A (en) * 2012-12-21 2015-08-31 닛토덴코 가부시키가이샤 Resin foam, and foam seal material
KR20190012349A (en) * 2017-07-27 2019-02-11 주식회사 휴비스 Foam sheet containing skin layer, preparation method thereof, and Food container comprising the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5940162B2 (en) * 1977-04-13 1984-09-28 株式会社クラレ Polyester foam molded product and its manufacturing method
GB8402514D0 (en) * 1984-01-31 1984-03-07 Scott Bader Co Unsaturated polyester foams
JP2003026845A (en) * 2001-07-11 2003-01-29 Kanegafuchi Chem Ind Co Ltd Foaming polyester resin composition
TW572961B (en) * 2001-07-11 2004-01-21 Kanegafuchi Chemical Ind Foamable polyester resin composition
WO2020004748A1 (en) * 2018-06-29 2020-01-02 주식회사 휴비스 Foamed sheet comprising calcium carbonate, manufacturing method therefor, and food container comprising same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0118112B1 (en) * 1988-12-01 1997-09-30 마쓰다 쇼헤이 Process for producing thermoplastic polyester resin foam
EP2612881A1 (en) * 2012-01-05 2013-07-10 Omya Development AG Fillers for foamed rigid polymer products
KR20150099390A (en) * 2012-12-21 2015-08-31 닛토덴코 가부시키가이샤 Resin foam, and foam seal material
KR20150078004A (en) * 2013-12-30 2015-07-08 도레이케미칼 주식회사 Microporous thermoplastic polymer resin foam with enhanced mechanical strength and foaming rate and the preparation thereof
KR20190012349A (en) * 2017-07-27 2019-02-11 주식회사 휴비스 Foam sheet containing skin layer, preparation method thereof, and Food container comprising the same

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