WO2021215697A1 - Composition de mélange maître et procédé de fabrication de feuille de mousse l'utilisant - Google Patents

Composition de mélange maître et procédé de fabrication de feuille de mousse l'utilisant Download PDF

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Publication number
WO2021215697A1
WO2021215697A1 PCT/KR2021/004150 KR2021004150W WO2021215697A1 WO 2021215697 A1 WO2021215697 A1 WO 2021215697A1 KR 2021004150 W KR2021004150 W KR 2021004150W WO 2021215697 A1 WO2021215697 A1 WO 2021215697A1
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Prior art keywords
resin
polyester resin
weight
dianhydride
masterbatch composition
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PCT/KR2021/004150
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English (en)
Korean (ko)
Inventor
이광희
허미
김우진
하상훈
최종한
Original Assignee
주식회사 휴비스
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Priority claimed from KR1020200048086A external-priority patent/KR102339308B1/ko
Priority claimed from KR1020200048084A external-priority patent/KR102339321B1/ko
Application filed by 주식회사 휴비스 filed Critical 주식회사 휴비스
Priority to CN202180003388.9A priority Critical patent/CN113853406A/zh
Priority to JP2021566053A priority patent/JP2022533925A/ja
Publication of WO2021215697A1 publication Critical patent/WO2021215697A1/fr

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    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • 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
    • 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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C08K5/1539—Cyclic anhydrides

Definitions

  • the present invention relates to a masterbatch composition usable for extrusion and foaming of a polyester resin, and a method for manufacturing a polyester resin foam sheet using the same.
  • Polyester resins with crystallinity such as polyethylene terephthalate (PET) have superior mechanical properties compared to polyethylene-based resins or polypropylene-based resins, and have excellent heat resistance and chemical resistance, and are used in various fields requiring light weight and high physical properties. This is possible. Polyester resin has excellent mechanical and chemical properties, so it can be used for multi-purpose applications, for example, conventionally for drinking water containers and medical, food packaging, food containers, sheets, films, automobile molded products, etc. applications are being made in the field of
  • PET polyethylene terephthalate
  • a foam sheet containing a polyester resin has a foaming 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 article as it is, and three-dimensional such as thermoforming It can be molded into a molded body having a typical shape.
  • crosslinking agents added for extrusion and foaming of polyester resin include dianhydrides such as pyromellitic dianhydride. There is a problem in that the thickening effect is not achieved due to thermal decomposition.
  • European Patent Registration No. 2009043 discloses a technique for preparing and injecting a crosslinking agent as a master batch.
  • PE low-melting-point polyethylene
  • the low-melting-point polyethylene which is the carrier resin of the masterbatch
  • the polyester resin which is a foaming resin
  • the present invention provides a masterbatch composition having improved compatibility of additives and mixing uniformity with a foaming resin, and a method for manufacturing a foam sheet having excellent foaming ratio and physical properties by using the same aims to provide
  • the masterbatch composition according to an embodiment of the present invention may contain 1 to 30% by weight of a carrier resin and a polyfunctional compound comprising 70 to 99% by weight of a polyester resin having a melting point of 200° C. or less.
  • the polyfunctional compound may have a structure in which the domain is dispersed in the matrix of the polyester resin.
  • 55 to 85% by weight of a polyester resin having a melting point of more than 200° C. and 10 to 40% by weight of a polyolefin resin may include 1 to 30% by weight of a carrier resin and a polyfunctional compound.
  • the polyolefin resin may be a linear low density polyethylene (LLDPE).
  • LLDPE linear low density polyethylene
  • the polyester resin may be polyethylene terephthalate (PET).
  • the polyethylene terephthalate may include an acid component including terephthalic acid and isophthalic acid; and a polymer of a diol component including at least one of ethylene glycol and diethylene glycol, and the content of isophthalic acid may be 10 to 30 mol% with respect to 100 mol% of the acid component.
  • the average particle size of the polyester resin is 600 ⁇ 2000 ⁇ m, the average particle size of 70% or more of the polyester resin may be 800 ⁇ 2000 ⁇ m.
  • the polyfunctional compound is pyromellitic dianhydride, benzophenone dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride , bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)thioether dianhydride, bisphenol A bisether dianhydride, 2,2-bis(3,4-dicarboxyphenyl) ) Hexafluoropropane dianhydride, 2,3,6,7-naphthalene-tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,2,5,6-naphthalene-tetracarboxylic dianhydride Water, 2,2',3,3'-biphenyltetracarboxylic dianhydride, hydroquinone bis
  • the masterbatch composition may further include a heat stabilizer.
  • the present invention also provides a method for producing a polyester resin foam sheet using the above-described masterbatch composition.
  • the manufacturing method of the foam sheet a masterbatch composition comprising 70 to 99% by weight of a polyester resin having a melting point of 200° C. or less and 1 to 30% by weight of a polyfunctional compound; a polyester resin having a melting point of 200 to 270°C; and mixing inorganic particles containing an alkaline earth metal carbonate to prepare a resin melt; and extruding and foaming the resin melt with an extruder.
  • the manufacturing method of the foam sheet is a masterbatch comprising 55 to 85% by weight of a polyester resin having a melting point of more than 200° C., 10 to 40% by weight of a polyolefin resin, and 1 to 30% by weight of a polyfunctional compound composition; a polyester resin having a melting point of 200 to 270°C; and mixing inorganic particles containing an alkaline earth metal carbonate to prepare a resin melt; and extruding and foaming the resin melt with an extruder.
  • the resin melt is 1 to 30% by weight of the masterbatch composition; 50 to 95% by weight of the polyester resin having a melting point of 200 to 270°C; and 1 to 30% by weight of the inorganic particles.
  • the alkaline earth metal element is at least one selected from the group consisting of Ca, Mg and Ba, and the average size of the inorganic particles may be 1 to 5 ⁇ m.
  • the foam sheet according to an embodiment of the present invention is manufactured by the above manufacturing method, and has an average foaming density according to KS M ISO 845:2012 of 100 to 600 kg/m 3 , and an average thickness may be 1.0 to 5.0 mm. .
  • the masterbatch composition according to an embodiment of the present invention contains a polyester resin as a main component together with a polyfunctional compound, so that uniform mixing with the polyester foaming resin can be achieved during extrusion and foaming of the polyester resin, and the generation of foreign substances is reduced can be removed.
  • a polyester resin as a main component together with a polyfunctional compound
  • first and second may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.
  • the singular expression includes the plural expression unless the context clearly dictates otherwise.
  • the present invention is mainly characterized in that the content of the polyolefin resin is controlled when a polyester resin having a melting point of 200° C. or less or a polyester resin having a melting point exceeding 200° C. is used as the carrier resin of the masterbatch composition.
  • a polyester resin is included as a carrier resin of the masterbatch composition.
  • the carrier resin is the same as the foaming resin, uniform mixing with the foaming resin can be achieved during extrusion and foaming of the foamed resin, and thermal decomposition of the polyfunctional compound can be suppressed during the extrusion and foaming process.
  • polyester having a melting point of 200° C. or less without a polyolefin resin when polyester having a melting point of 200° C. or less without a polyolefin resin is used as a carrier resin, it also provides an advantage of removing polyethylene foreign substances generated on a die and a mandrel during extrusion and foaming.
  • the masterbatch composition according to an embodiment of the present invention may include a polyester resin having a melting point of 200° C. or less and a polyfunctional compound.
  • the polyester resin having a melting point of 200° C. or less corresponds to a component used for mixing and commercialization to impart compatibility as a carrier resin
  • the polyfunctional compound corresponds to a compound that improves the viscosity of the foamed resin.
  • the melting point of the polyester resin may be 200° C. or less, specifically 180° C. or less, and more specifically 150° C. or less.
  • the content of the polyester resin having a melting point of 200° C. or less may be 70 to 99% by weight, specifically 70 to 95% by weight, and more specifically 70 to 90% by weight based on the total weight of the masterbatch composition.
  • the content of the polyester resin is less than 70% by weight, it may cause a non-uniform mixing with the foaming resin, thereby reducing the physical properties of the resulting foam, and if the content exceeds 99% by weight, the master batch Since the content of the added polyfunctional compound is lowered, the effect of improving the viscosity of the foamed resin may be insignificant.
  • the polyfunctional compound may have a structure in which domains are dispersed on a matrix of a polyester resin. Even if a homogeneous material compatible with the polyester resin, which is a foaming resin, is used as the matrix of the masterbatch composition, when a polyester resin other than a polyfunctional compound is included as a domain, the polyester resin as a domain is dispersed in the masterbatch manufacturing process When present, there is a possibility of inhibiting the dispersibility of the polyfunctional compound. However, by having a structure containing 1 to 30% by weight of a polyfunctional compound as a domain dispersed in a matrix containing 70 to 99% by weight of a polyester resin having a melting point of 200° C. or less, uniform dispersion of the polyfunctional compound is possible .
  • the masterbatch composition according to another embodiment of the present invention may include a polyester resin, a polyolefin resin, and a polyfunctional compound having a melting point of more than 200°C.
  • polyester resins and polyolefin resins having a melting point of more than 200 ° C. correspond to components used for mixing and commercialization to impart compatibility as a carrier resin
  • polyfunctional compounds correspond to compounds that improve the viscosity of the foamed resin.
  • the melting point of the polyester resin may be greater than 200 °C, specifically 200 ⁇ 270 °C.
  • the masterbatch composition includes a polyester resin as a carrier resin.
  • the carrier resin of the masterbatch composition is the same as the foaming resin, uniform mixing with the foaming resin can be achieved during extrusion and foaming of the foamed resin.
  • the content of the polyester resin may be 55 to 85% by weight, specifically 60 to 85% by weight, and more specifically 70 to 85% by weight based on the total weight of the masterbatch composition. If the content of the polyester resin is less than 55% by weight, it may cause a non-uniform mixing with the foaming resin, thereby reducing the physical properties of the resulting foam, and if the content exceeds 85% by weight, the master batch Since the content of the added polyfunctional compound is lowered, the effect of improving the viscosity of the foamed resin may be insignificant.
  • the masterbatch composition includes a polyolefin resin as a carrier resin.
  • the content of the polyolefin resin may be 10 to 40% by weight, specifically 10 to 30% by weight, more specifically 10 to 20% by weight based on the total weight of the masterbatch composition.
  • the content of the polyolefin resin is less than 10% by weight, the processability and moldability of the masterbatch composition may be reduced, and when the content exceeds 40% by weight, the content of the polyolefin resin, which is a material different from the foamed resin, increases, so that the foamed resin The physical properties of the expanded molded article may be deteriorated by causing non-uniform mixing with the .
  • polyolefin resins are selected from the group consisting of low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE) and polypropylene (PP).
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • HDPE high-density polyethylene
  • PP polypropylene
  • the polyolefin resin is a linear low density polyethylene.
  • polyester resin of the present invention examples include an aromatic or aliphatic polyester resin synthesized from a dicarboxylic acid component, a glycol component, or hydroxycarboxylic acid.
  • Non-limiting examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polylactic acid (PLA), polyglycolic acid (PGA). , at least one selected from the group consisting of polyethylene adipate (Polyehtyleneadipate, PEA), polyhydroxyalkanoate (PHA), polytrimethylene terephthalate (PTT) and polyethylene naphthalate (PEN).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PLA polylactic acid
  • PGA polyglycolic acid
  • PEA polyethylene adipate
  • PHA polyhydroxyalkanoate
  • PTT polytrimethylene terephthalate
  • PEN polyethylene naphthalate
  • polyethylene terephthalate may be used as the polyester resin.
  • the polyethylene terephthalate may include an acid component including terephthalic acid and isophthalic acid; And it may be a polymer of a diol component comprising at least one of ethylene glycol and diethylene glycol.
  • the content of isophthalic acid may be 10 to 30 mol%.
  • the polyester resin may have an intrinsic viscosity (IV) of 0.4 dl/g to 1.2 dl/g. Specifically, the intrinsic viscosity is 0.5 dl/g to 1.1 dl/g, 0.6 dl/g to 1.0 dl/g, 0.7 dl/g to 1.1 dl/g, 0.9 dl/g to 1.1 dl/g, 0.5 dl/g to 0.7 dl/g, 0.6 dl/g to 0.7 dl/g, 0.7 dl/g to 0.9 dl/g, 0.75 dl/g to 0.85 dl/g, 0.77 dl/g to 0.83 dl/g or 0.6 dl/g to It may be 0.8 dl/g.
  • the average particle size of the polyester resin in the masterbatch composition may be 600 ⁇ 2,000 ⁇ m, specifically 800 ⁇ 2,000 ⁇ m, more specifically 1,000 ⁇ 2,000 ⁇ m. If the average particle size of the polyester resin in the masterbatch composition is less than the above range, especially when it is less than 800 ⁇ m, the particle size of the polyester resin is too small, so that it is not easy to handle in the masterbatch manufacturing process.
  • the average particle size of 70% or more of the polyester resin may be 800 to 2,000 ⁇ m, specifically 1,000 to 2,000 ⁇ m, and more specifically 1,200 to 2,000 ⁇ m.
  • the masterbatch composition includes a polyfunctional compound that improves the viscosity by crosslinking with the foaming resin.
  • the content of the polyfunctional compound may be 1 to 30% by weight, specifically 5 to 30% by weight, more specifically 10 to 30% by weight, based on the total weight of the masterbatch composition. .
  • the content of the polyfunctional compound is less than 1% by weight, the effect of improving the viscosity of the foamed resin may be insignificant, and when the content exceeds 30% by weight, the processability of the masterbatch composition may be reduced.
  • Such polyfunctional compounds include pyromellitic anhydride (PMDA), benzophenone dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 3,3',4,4' -Biphenyltetracarboxylic acid dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)thioether dianhydride, bisphenol A bisether dianhydride, 2,2-bis( 3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,3,6,7-naphthalene-tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,2,5, 6-naphthalene-tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, hydroquinone bisether
  • the melting point of the polyfunctional compound may be 270°C or higher, and specifically, 270°C to 350°C, 270°C to 330°C, 270°C to 310°C, or 270°C to 290°C.
  • the melting point may be 280 ⁇ 5°C.
  • the masterbatch composition of the present invention may further include conventionally known additives, for example, antioxidants, heat stabilizers, fillers, refractory materials, mold release agents, colorants and other materials in order to improve the processability or physical properties of the resin.
  • a heat stabilizer may be used as an additive.
  • the heat stabilizer may include a pentavalent and/or trivalent phosphorus compound, or a phenol-based compound having a large chemical structural steric hindrance.
  • the pentavalent and/or trivalent phosphorus compound may include trimethylphosphite, phosphoric acid, phosphorous acid, tris(2,4-di-tert-butylphenyl)phosphite, and the like, and a phenolic compound having a large chemical structural steric hindrance.
  • the compound is pentaerythritol-tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propion ester (Pentaerythritol tetrakis (3- (3,5-di-tertbutyl-4-hydroxyphenyl) propionate, Irganox 1010), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (1,1,3-tris(2-methyl-4-hydroxy-5-tert- butylphenyl)butane), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ), N,N'-hexamethylenebis(3,5-tert-butyl-4-hydroxyhydrocinnamamide) (N,N'-
  • the masterbatch composition may have the form of pellets, granules, beads, chips, and the like, and in some cases may have a powder form.
  • the average size is not particularly limited, but in the case of pellets, the length of the pellets may be 3 to 6 mm for the uniformity of cells formed in the foam.
  • the method for producing a masterbatch composition comprises the steps of pulverizing a polyester resin having a melting point of 200 °C or less; and extruding the pulverized polyester resin and the polyfunctional compound with an extruder to pelletize.
  • a method for producing a masterbatch composition comprises the steps of pulverizing a polyester resin having a melting point of more than 200°C; and extruding the pulverized polyester resin, polyolefin resin, and polyfunctional compound with an extruder to pelletize.
  • the step of pulverizing the polyester resin may be a step of pulverizing the average particle size of the polyester resin to 600 to 2,000 ⁇ m.
  • the average particle size of 70% or more of the polyester resin may be 800 to 2,000 ⁇ m.
  • the pelletizing process temperature may be less than 200 °C, specifically 180 ⁇ 190 °C.
  • the pelletizing process temperature is lower than the melting point of the polyfunctional compound, which is a domain of the masterbatch composition, and is higher than the melting point of the polyester resin as a matrix. Accordingly, the polyfunctional compound as a domain in the pelletized masterbatch can be uniformly dispersed in the polyester resin as a matrix. In addition, the polyfunctional compound is not melted in the process of being pelletized, thereby preventing the polyester resin from reacting with the polyfunctional compound, thereby preventing the polyfunctional compound from being thermally decomposed.
  • the pelletizing process temperature is lower than the melting point of the polyester resin and the polyfunctional compound of the masterbatch composition, and the polyolefin resin It is a temperature higher than the melting point. Accordingly, the polyester resin in the pelletized masterbatch can maintain the average particle size in the above-mentioned pulverizing step. In addition, the polyester resin and the polyfunctional compound are not melted in the process of being pelletized, thereby preventing the polyester resin from reacting with the polyfunctional compound, and thus preventing the polyfunctional compound from being thermally decomposed.
  • the present invention also provides a method for manufacturing a foam sheet using the above-described masterbatch composition.
  • a method of manufacturing a foam sheet according to an embodiment includes a masterbatch composition comprising a polyester resin and a polyfunctional compound having a melting point of 200° C. or less; a polyester resin having a melting point of 200 to 270°C; and mixing inorganic particles containing an alkaline earth metal carbonate to prepare a resin melt; incorporating a blowing agent into the resin melt to form a foamable melt; and extruding the foamable melt.
  • a method for manufacturing a foam sheet according to another embodiment includes a masterbatch composition comprising a polyester resin, a polyolefin resin and a polyfunctional compound having a melting point of more than 200°C; a polyester resin having a melting point of 200 to 270°C; and mixing inorganic particles containing an alkaline earth metal carbonate to prepare a resin melt; incorporating a blowing agent into the resin melt to form a foamable melt; and extruding and foaming the foamable melt to prepare a foam sheet.
  • Preparing the resin melt may be performed at a temperature of 260 ⁇ 300 °C.
  • the resin melt is 1-30% by weight of the masterbatch composition; 50 to 95% by weight of a polyester resin having a melting point of 200 to 270°C; and 1 to 30% by weight of inorganic particles.
  • the content of the masterbatch composition may be 1 to 30% by weight, specifically 1 to 10% by weight, based on the total weight of the resin melt. At this time, when the content of the masterbatch composition is less than 1% by weight, it is difficult to express the desired effect of improving the viscosity of the foamed resin, and when it exceeds 30% by weight, problems such as deterioration of workability may occur.
  • the polyester resin may be at least one selected from the group consisting of aromatic and aliphatic polyester resins synthesized from a dicarboxylic acid component and a glycol component or hydroxycarboxylic acid. Examples of the polyester resin are as described above. In addition, the polyester resin may have the form of pellets, granules, beads, chips, and the like, and in some cases may be in the form of powder.
  • the resin melt contains alkaline earth metal carbonate
  • the cell size of the foam sheet can be reduced and the density can be increased, the sheet surface is uniform to reduce the occurrence of corrugation, and excellent thermoformability can be exhibited.
  • calcium carbonate is uniformly distributed in the polyester resin, the foam sheet obtained by extruding and foaming the resin has high thermal conductivity, so that it is possible to solve the problem of tearing the foam sheet during molding of the foam sheet.
  • the alkaline earth metal carbonate 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 include calcium carbonate may include
  • 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.
  • inorganic particles containing alkaline earth metal carbonate may be mixed with a polyester resin and a masterbatch composition in the form of a masterbatch to prepare a resin melt.
  • the step of extruding foaming comprises a hydrophilic agent, a heat stabilizer, a waterproofing agent, a cell size enlarger, an infrared damping agent, a plasticizer, a fire protection chemical, a pigment, an elastomeric polymer, an extrusion aid, an antioxidant, an antistatic agent and a UV absorber.
  • One or more additives selected from the group may be introduced into the fluid connection line.
  • additives not added during the fluid connection line may be added during the extrusion process.
  • 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 It may include mixtures such as a mixture series of , a mixture series of polyols and polyurethane resins, a mixture series of acrylic polymers and polyurethane resins, polyimide series, and a mixture series of cyanoacrylate and urethane.
  • blowing agent examples include physical blowing agents such as N 2 , CO 2 , Freon, butane, pentane, neopentane, hexane, isohexane, heptane, isoheptane, and methyl chloride.
  • butane may be used in the present invention. have.
  • the step of extrusion foaming may be performed by cooling the foamable melt at 220° C. to 260° C. for easy foaming, and then passing the cooled foamable melt through a die (Dei).
  • the intrinsic viscosity of the foamable melt may be in the range of 0.9 dl/g or more, 1.2 dl/g to 1.5 dl/g.
  • the average foaming density according to KS M ISO 845:2012 of the manufactured foam sheet is 100 to 600 kg/m 3 , 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 average thickness of the foam sheet may be in the range of 1.0 to 5.0mm.
  • the average thickness of the foam sheet is 1.0 to 4.0mm, 1.0 to 3.5mm, 1.0 to 3.0mm, 1.0 to 5.5mm, 1.0 to 2.0mm, 1.0 to 1.5mm, 1.5 to 5.0mm, 2.0 to 5.0mm , 3.0 to 5.0 mm, or 4.0 to 5.0 mm.
  • Polyethylene terephthalate (PET) having a melting point of 180° C. was dried at 130° C. to remove moisture, and pulverized to have an average particle size of 600 to 2,000 ⁇ m. At this time, the average particle size of 70% or more of the pulverized PET was 800 to 2,000 ⁇ m. Thereafter, a composition was prepared by mixing 89.9% by weight of pulverized PET, 10% by weight of pyromellitic dianhydride (PMDA), and 0.1% by weight of a heat stabilizer (Iganox 1010), and the prepared composition was pelleted at 185° C. using an extruder. to prepare a masterbatch.
  • PMDA pyromellitic dianhydride
  • Iganox 1010 a heat stabilizer
  • Each masterbatch was prepared in the same manner as in Preparation Example 1, except that the melting point of PET was adjusted as shown in Table 1 below.
  • Polyethylene terephthalate (PET) having a melting point of 250° C. was dried at 130° C. to remove moisture, and pulverized to have an average particle size of 600 to 2,000 ⁇ m. At this time, the average particle size of 70% or more of the pulverized PET was 800 to 2,000 ⁇ m. Then, 60% by weight of pulverized PET, 29.9% by weight of linear low-density polyethylene (LLDPE), 10% by weight of pyromellitic dianhydride (PMDA) and 0.1% by weight of a heat stabilizer (Iganox 1010) were mixed to prepare a composition, and prepared The composition was pelletized at 185°C using an extruder to prepare a masterbatch.
  • LLDPE linear low-density polyethylene
  • PMDA pyromellitic dianhydride
  • Iganox 1010 a heat stabilizer
  • Each master batch was prepared in the same manner as in Preparation Example 4, except that the contents of PET and LLDPE were adjusted as shown in Table 1 below.
  • the pulverized PET having an average particle size of 100 to 300 ⁇ m and an average particle size of 80% or more of the pulverized PET was 100 to 200 ⁇ m was used. Thereafter, each masterbatch was prepared in the same manner as in Preparation Example 4, except that the content of PET and LLDPE was adjusted as shown in Table 1 below.
  • polyester foam sheet In order to prepare the polyester foam sheet, first, 100 parts by weight of polyethylene terephthalate (PET) resin was dried at 180° C. to remove moisture, and 92.5 wt % of PET resin from which moisture was removed in an extruder, masterbatch prepared in Preparation Example 1 4.5% by weight of the composition and 3% by weight of calcium carbonate having an average particle size of 1.0 to 5.0 ⁇ m were mixed, and heated to 280° C. to prepare a resin melt. Then, 1.5 parts by weight of butane as a foaming agent was added to the extruder based on 100 parts by weight of PET resin, and the resin melt was cooled to 250 ⁇ 2°C. The cooled resin melt was extruded while passing through a die, 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 .
  • PET polyethylene terephthalate
  • Foam sheets were each prepared in the same manner as in Example 1, except that the master batch compositions prepared in Preparation Examples 2 to 6 were respectively used instead of the master batch composition prepared in Preparation Example 1.
  • Foam sheets were each prepared in the same manner as in Example 1, except that the master batch compositions prepared in Comparative Preparation Examples 1 and 2 were used instead of the master batch composition prepared in Preparation Example 1, respectively.
  • the overall width of each foam sheet was divided into 8 at regular intervals and the thickness was measured using an indicator (ID-C112, Mitutoyo Corporation), and then the average value was calculated.
  • the foaming fairness of the foam sheet was evaluated with the uniformity of the measured density after measuring the density by selecting a plurality of samples at random among the produced foam sheets. Specifically, from 30 minutes after the start of foam sheet production to the end of production, 10 samples were randomly selected and the density was measured in the same manner as described above, and a deviation was derived based on the average density value of the 10 samples measured.
  • Example 1 1.2 2.0 330 2 ⁇ 0.5 does not exist
  • Example 2 1.1 2.2 330 3 ⁇ 0.5 does not exist
  • Example 3 1.1 2.0 340 4 ⁇ 0.5 does not exist
  • Example 4 1.2 2.0 330 2 ⁇ 0.5 handful
  • Example 5 1.1 2.2 330 3 ⁇ 0.5 handful
  • Example 6 1.1 2.0 340 4 ⁇ 0.5 handful Comparative Example 1 1.0 2.0 350 12 ⁇ 0.5 much Comparative Example 2 1.0 2.0 330 5 ⁇ 0.5 much
  • the masterbatch composition according to Preparation Examples 1 to 6 contains a polyester resin (PET) as a main component together with a polyfunctional compound (PMDA), thereby extruding and foaming the polyester resin.
  • PET polyester resin
  • PMDA polyfunctional compound
  • the foam sheets according to Examples 1 to 6 showed a lower density deviation compared to Comparative Example 1. This prevents thermal decomposition of the additives mixed in the resin melt during extrusion and foaming of the polyester resin, thereby confirming that the process stability is excellent and the foaming ratio of the manufactured foam sheet is excellent.
  • the masterbatch composition includes polyethylene resin (LLDPE), but by including polyester resin (PET) as a main component, foreign substances generated on the die and mandrel of the foaming device compared to Comparative Examples 1 and 2 It was found that only a small amount of
  • the masterbatch composition according to an embodiment of the present invention contains a polyester resin as a main component together with a polyfunctional compound, so that uniform mixing with the polyester foaming resin can be achieved during extrusion and foaming of the polyester resin, and the generation of foreign substances is reduced can be removed.
  • a polyester resin as a main component together with a polyfunctional compound

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

Abstract

La présente invention concerne une composition de mélange maître utilisable dans l'extrusion et le moussage d'une résine de polyester, et un procédé de production d'une feuille de mousse de résine de polyester l'utilisant. Plus précisément, la composition de mélange maître comprend : une résine de base ; et 1 à 30 % en poids d'un composé polyfonctionnel, la résine de base pouvant comprendre de 70 à 99 % en poids d'une résine de polyester ayant un point de fusion inférieur ou égal à 200 °C, ou 55 à 85 % en poids d'une résine de lyester ayant un point de fusion supérieur à 200 °C, et 10 à 40 % en poids d'une résine de polyoléfine.
PCT/KR2021/004150 2020-04-21 2021-04-02 Composition de mélange maître et procédé de fabrication de feuille de mousse l'utilisant WO2021215697A1 (fr)

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JP2021566053A JP2022533925A (ja) 2020-04-21 2021-04-02 マスターバッチ組成物及びこれを用いた発泡シートの製造方法

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KR1020200048084A KR102339321B1 (ko) 2020-04-21 2020-04-21 마스터배치 조성물 및 이를 이용한 발포시트의 제조방법
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2009043A1 (fr) * 2007-06-27 2008-12-31 Point Plastic S.r.l. Concentré de composés polyfonctionnels utilisables pour la préparation de matériaux de mousse de polyester
EP2343330A1 (fr) * 2010-01-12 2011-07-13 Armacell Enterprise GmbH Mélanges maîtres fortement concentrés comprenant des composés multifonctions pour le processus d'expansion de polyester
KR20170080998A (ko) * 2015-12-31 2017-07-11 주식회사 휴비스 마스터배치 조성물 및 이를 이용한 폴리에스테르 수지 발포체의 제조방법
JP2019108507A (ja) * 2017-12-20 2019-07-04 株式会社カネカ 熱膨張性マイクロカプセルのマスターバッチ
KR20200002330A (ko) * 2018-06-29 2020-01-08 주식회사 휴비스 성형성이 우수한 발포시트, 이의 제조방법 및 이를 이용한 식품용기

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004263077A (ja) * 2003-03-03 2004-09-24 Mitsubishi Polyester Film Copp 熱可塑性ポリエステル樹脂発泡フィルムの製造方法
JP2006528991A (ja) * 2003-05-19 2006-12-28 ポリマーズ オーストラリア プロプライアタリー リミティド ポリエステルマスターバッチ組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2009043A1 (fr) * 2007-06-27 2008-12-31 Point Plastic S.r.l. Concentré de composés polyfonctionnels utilisables pour la préparation de matériaux de mousse de polyester
EP2343330A1 (fr) * 2010-01-12 2011-07-13 Armacell Enterprise GmbH Mélanges maîtres fortement concentrés comprenant des composés multifonctions pour le processus d'expansion de polyester
KR20170080998A (ko) * 2015-12-31 2017-07-11 주식회사 휴비스 마스터배치 조성물 및 이를 이용한 폴리에스테르 수지 발포체의 제조방법
JP2019108507A (ja) * 2017-12-20 2019-07-04 株式会社カネカ 熱膨張性マイクロカプセルのマスターバッチ
KR20200002330A (ko) * 2018-06-29 2020-01-08 주식회사 휴비스 성형성이 우수한 발포시트, 이의 제조방법 및 이를 이용한 식품용기

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