CN113853406A - Masterbatch composition and method for producing foamed sheet using same - Google Patents

Masterbatch composition and method for producing foamed sheet using same Download PDF

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Publication number
CN113853406A
CN113853406A CN202180003388.9A CN202180003388A CN113853406A CN 113853406 A CN113853406 A CN 113853406A CN 202180003388 A CN202180003388 A CN 202180003388A CN 113853406 A CN113853406 A CN 113853406A
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China
Prior art keywords
resin
polyester resin
dianhydride
melting point
master batch
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CN202180003388.9A
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Chinese (zh)
Inventor
李光熙
许娓
金宇镇
河相勋
崔钟汉
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Huvis Corp
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Huvis Corp
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Publication date
Priority claimed from KR1020200048086A external-priority patent/KR102339308B1/en
Priority claimed from KR1020200048084A external-priority patent/KR102339321B1/en
Application filed by Huvis Corp filed Critical Huvis Corp
Publication of CN113853406A publication Critical patent/CN113853406A/en
Withdrawn legal-status Critical Current

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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

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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

The present invention relates to a masterbatch composition that can be used for extrusion and foaming of a polyester resin, and a method for producing a polyester resin foamed sheet using the masterbatch composition. Specifically, the masterbatch composition comprises a carrier resin and 1 to 30 wt% of a polyfunctional compound, and the carrier resin may comprise 70 to 99 wt% of a polyester resin having a melting point of 200 ℃ or less, or 55 to 85 wt% of a polyester resin having a melting point of more than 200 ℃ and 10 to 40 wt% of a polyolefin resin.

Description

Masterbatch composition and method for producing foamed sheet using same
Technical Field
The present invention relates to a masterbatch composition usable for extrusion and foaming of a polyester resin, and a method for producing a polyester resin foamed sheet using the masterbatch composition.
Background
Polyester resins having crystallinity such as polyethylene terephthalate (PET) have excellent mechanical properties, heat resistance, chemical resistance and the like, compared with polyethylene resins, polypropylene resins and the like, and thus can be applied to various fields requiring light weight and high physical properties. Polyester resins (polyester resins) are excellent in mechanical properties and chemical properties and therefore have been used in various applications, for example, in the fields of drinking water containers, medical applications, food packaging papers, food containers, sheets (sheets), films (films), automotive moldings, and the like.
In particular, a foamed sheet containing a polyester resin has a foamed layer composed of a resin composition containing a polyester resin, and therefore is excellent in lightweight property and strength, and can be used not only as it is as a sheet-shaped molded article but also molded into a molded article having a three-dimensional shape by thermoforming or the like.
In the case of molding a polymer resin by continuous extrusion foaming, although it is important to adjust the viscosity of the molten resin, the polyester resin has the following problems compared with the conventional foamed resin: the melt viscosity is low and additives have to be mixed for viscosity control in order to increase the viscosity. Further, as the crosslinking agent to be added for extrusion and foaming of the polyester resin, dianhydride such as pyromellitic dianhydride is exemplified, but when the above compound is directly fed into an extruder, there is a problem that the particles stick to a screw or a cylinder and are not reacted and thermally decomposed, and a thickening effect cannot be obtained.
In order to solve such a problem, european patent No. 2009043 discloses a technique in which a crosslinking agent is prepared as a master batch and then introduced. However, the addition of a large amount of low-melting Polyethylene (PE) contained as a base resin of the master batch causes uneven mixing with the polyester resin, and thus there is a limitation that the physical properties of the foamed molded article produced therefrom are deteriorated. Further, since the low-melting polyethylene as the carrier resin of the master batch is incompatible with the polyester resin as the foaming resin, there is a problem that foreign matter of the low-melting polyethylene is generated in the die (die) and the mandrel (mandrel) during extrusion foaming, and therefore, there is a problem that the foaming device needs to be periodically cleaned.
Disclosure of Invention
Problems to be solved by the invention
In order to solve the problems of the prior art as described above, an object of the present invention is to provide a masterbatch composition improved in compatibility with additives and mixing uniformity with a foamable resin, and a method for producing a foamed sheet excellent in foaming ratio and physical properties by using the masterbatch composition.
Means for solving the problems
The masterbatch composition of an embodiment of the present invention may comprise: 70 to 99 wt% of a carrier resin containing a polyester resin having a melting point of 200 ℃ or lower, and 1 to 30 wt% of a polyfunctional compound.
In this case, the polyfunctional compound may have a structure in which domains are dispersed in the matrix of the polyester resin.
In another example, the method may include: the resin composition comprises 55 to 85 wt% of a carrier resin comprising a polyester resin having a melting point of more than 200 ℃ and 10 to 40 wt% of a polyolefin resin, and 1 to 30 wt% of a polyfunctional compound.
In this case, the polyolefin resin may be Linear Low Density Polyethylene (LLDPE).
On the other hand, the polyester resin may be Polyethylene Terephthalate (PET).
The polyethylene terephthalate may be a polymer containing an acid component of terephthalic acid and isophthalic acid and a diol component of at least 1 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 may be 600 to 2000 μm, and 70% or more of the average particle size of the polyester resin may be 800 to 2000 μm.
The polyfunctional compound may be selected from the group consisting of pyromellitic dianhydride, benzophenone dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, bis (3, 4-dicarboxyphenyl) sulfide dianhydride, bisphenol a bisether dianhydride, 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 ', 3, 3' -biphenyltetracarboxylic dianhydride, hydroquinone diether dianhydride, bis (3, 4-dicarboxyphenyl) sulfoxide dianhydride, and 3,4,9, 10-perylenetetracarboxylic dianhydride.
In addition, the masterbatch composition may further include a heat stabilizer.
The present invention provides a method for producing a polyester resin foamed sheet using the master batch composition.
In one example, the method for producing the foamed sheet may include: a step of mixing a master batch composition comprising 70 to 99 wt% of a polyester resin having a melting point of 200 ℃ or lower and 1 to 30 wt% of a polyfunctional compound, the polyester resin having a melting point of 200 to 270 ℃, and inorganic particles containing an alkaline earth metal carbonate to produce a resin melt; and a step of extruding and foaming the resin melt by an extruder.
In another example, the method for manufacturing the foamed sheet may include: a step of mixing a master batch composition, a polyester resin having a melting point of 200 to 270 ℃, and inorganic particles containing an alkaline earth metal carbonate to produce a resin melt, wherein the master batch composition comprises 55 to 85 wt% of the polyester resin having a melting point of more than 200 ℃,10 to 40 wt% of a polyolefin resin, and 1 to 30 wt% of a polyfunctional compound; and a step of extruding and foaming the resin melt by an extruder.
The resin melt may include: 1 to 30 wt% of the masterbatch composition, 50 to 95 wt% of the polyester resin having a melting point of 200 to 270 ℃, and 1 to 30 wt% of the inorganic particles.
The alkaline earth metal element may be 1 or more selected from the group consisting of Ca, Mg and Ba, and the inorganic particles may have an average size of 1 to 5 μm.
On the other hand, the foamed sheet according to an embodiment of the present invention may be produced by the above-described production method, and the average foaming density according to KS M ISO 845:2012 may be 100 to 600kg/M3The average thickness may be 1.0 to 5.0 mm.
ADVANTAGEOUS EFFECTS OF INVENTION
The master batch composition according to the embodiment of the present invention contains the polyester resin as a main component together with the polyfunctional compound, so that the master batch composition can be uniformly mixed with the polyester foaming resin during extrusion and foaming of the polyester resin, and the generation of foreign substances can be removed. In addition, thermal decomposition of the additive mixed into the resin melt can be prevented at the time of extrusion and foaming of the polyester resin. Therefore, the process stability is excellent, and the foam sheet produced has an advantage of excellent expansion ratio.
Detailed Description
The present invention may be modified in various ways. Accordingly, specific embodiments are illustrated in the drawings and are described herein in detail. However, the present invention is not limited to the specific embodiments disclosed, but should be understood to include all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.
In the present application, terms such as "including" or "having" mean that the features, numerals, steps, actions, constituents, elements, or combinations thereof described in the specification exist, and it should be understood that the possibility of existence or addition of one or more other features, numerals, steps, actions, constituents, elements, or combinations thereof is not excluded in advance. In addition, the terms 1,2, etc. may be used to describe various constituent elements, but the constituent elements are not limited by the terms. The above terms are used only for the purpose of distinguishing one constituent element from other constituent elements. For example, the 1 st component may be designated as the 2 nd component, and the 2 nd component may be designated as the 1 st component similarly, without departing from the scope of the present invention. To the extent that no difference in context is intended, an expression in the singular encompasses more than 2 expressions.
Hereinafter, examples of the present invention will be described in more detail.
In the case of using a polyester resin having a melting point of 200 ℃ or less or a polyester resin having a melting point of more than 200 ℃ as a carrier resin of the master batch composition, the present invention is mainly characterized by controlling the content of the polyolefin resin.
Specifically, as the carrier resin of the masterbatch composition, a polyester resin is contained. Since the carrier resin is the same as the foamable resin, it can be uniformly mixed with the foamable resin during extrusion and foaming of the foamable resin, and thermal decomposition of the polyfunctional compound can be suppressed during extrusion and foaming.
In addition, in the case where a polyester having a melting point of 200 ℃ or lower is used as the carrier resin without a polyolefin resin, there is provided an advantage that polyethylene foreign matter generated at the die (die) and the mandrel (mandrel) during extrusion foaming can be removed.
The masterbatch composition according to an embodiment of the present invention may further include a polyester resin having a melting point of 200 ℃ or lower and a polyfunctional compound. In this case, the polyester resin having a melting point of 200 ℃ or lower is a carrier resin and is a component for mixing and producing products for the purpose of imparting compatibility, and the polyfunctional compound corresponds to a compound for increasing the viscosity of the foamed resin. Here, the melting point of the polyester resin may be 200 ℃ or less, specifically 180 ℃ or less, more specifically 150 ℃ or less.
The content of the polyester resin having a melting point of 200 ℃ or lower may be 70 to 99% by weight, specifically 70 to 95% by weight, more specifically 70 to 90% by weight, based on the weight of the entire masterbatch composition. When the content of the polyester resin is less than 70% by weight, the mixing with the foamable resin becomes uneven, and the physical properties of the foam produced therefrom may be deteriorated, while when the content is more than 99% by weight, the content of the polyfunctional compound added to the master batch is decreased, and the effect of increasing the viscosity of the foamable resin is insignificant.
Specifically, the polyester resin may have a structure in which a polyfunctional compound is dispersed as domains in a matrix of the polyester resin. Even if the same material compatible with the polyester resin as the foamable resin is used as the matrix of the masterbatch composition, when the polyester resin other than the polyfunctional compound is contained as the domain, the polyester resin as the domain exists in a dispersed state in the production process of the masterbatch, and therefore, the dispersibility of the polyfunctional compound may be inhibited. However, the polyfunctional compound can be uniformly dispersed by having a structure in which 1 to 30% by weight of the polyfunctional compound is dispersed as domains in a matrix comprising 70 to 99% by weight of a polyester resin having a melting point of 200 ℃ or less.
The masterbatch composition according to another embodiment of the present invention may include a polyester resin having a melting point of more than 200 ℃, a polyolefin resin, and a polyfunctional compound. In this case, the polyester resin and the polyolefin resin having melting points of more than 200 ℃ are components used for mixing and production for the purpose of imparting compatibility, and the polyfunctional compound corresponds to a compound for increasing the viscosity of the foamed resin. The melting point of the polyester resin may be more than 200 ℃, specifically 200 to 270 ℃.
First, the masterbatch composition comprises a polyester resin as a carrier resin. Since the carrier resin and the foamable resin of the master batch composition are the same, they can be uniformly mixed with the foamable resin at the time of extrusion and foaming of the foamable resin.
The content of the polyester resin may be 55 to 85% by weight, specifically 60 to 85% by weight, more specifically 70 to 85% by weight, based on the weight of the entire master batch composition. When the content of the polyester resin is less than 55% by weight, the following problems may occur: resulting in uneven mixing with the foaming resin and a decrease in the physical properties of the foam produced therefrom. When the content is more than 85% by weight, the content of the polyfunctional compound added to the master batch decreases, and the effect of increasing the viscosity of the foamed resin is insignificant.
In addition, the masterbatch composition comprises a polyolefin resin as a carrier resin.
The polyolefin resin may be contained in an amount of 10 to 40% by weight, specifically 10 to 30% by weight, more specifically 10 to 20% by weight, based on the weight of the entire masterbatch composition. When the content of the polyolefin resin is less than 10% by weight, the processability and moldability of the master batch composition may be lowered. When the content is more than 40% by weight, the content of the polyolefin resin, which is a substance different from the foamed resin, is increased, resulting in non-uniform mixing with the foamed resin and a decrease in the physical properties of the foamed molded article.
As examples of such polyolefin resins, 1 or more selected from the group consisting of Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE), and Polypropylene (PP) may be cited. For example, the polyolefin resin is linear low density polyethylene.
The polyester resin of the present invention may be an aromatic or aliphatic polyester resin synthesized from a dicarboxylic acid component and a diol component or hydroxycarboxylic acid. As non-limiting examples of the polyester resin, 1 or more selected from the group consisting of Polyethylene Terephthalate (PET), Polybutylene Terephthalate (PBT), polylactic acid (PLA), Polyglycolic acid (PGA), Polyethylene adipate (PEA), Polyhydroxyalkanoate (PHA), Polytrimethylene Terephthalate (PTT), and Polyethylene naphthalate (PEN) may be cited.
Specifically, in the present invention, polyethylene terephthalate can be used as the polyester resin. In this case, the polyethylene terephthalate may be a polymer containing an acid component of terephthalic acid and isophthalic acid and a diol component of 1 or more of ethylene glycol and diethylene glycol. The content of isophthalic acid may be 10 to 30 mol% with respect to 100 mol% of the acid component.
The Intrinsic Viscosity (IV) of the polyester resin may be 0.4dL/g to 1.2 dL/g. Specifically, the intrinsic viscosity may be 0.5dL/g to 1.1dL/g, 0.6dL/g to 1.0dL/g, 0.7dL/g to 1.1dL/g, 0.9dL/g to 1.1dL/g, 0.5dL/g to 0.7dL/g, 0.6dL/g to 0.7dL/g, 0.7dL/g to 0.9dL/g, 0.75dL/g to 0.85dL/g, 0.77dL/g to 0.83dL/g, or 0.6dL/g to 0.8 dL/g.
On the other hand, the average particle size of the polyester resin in the masterbatch composition may be 600 to 2000. mu.m, specifically 800 to 2000. mu.m, and more specifically 1000 to 2000. mu.m. If the average particle size of the polyester resin in the masterbatch composition is smaller than the above range, particularly smaller than 800. mu.m, the particle size of the polyester resin is too small, which is a problem that handling in the masterbatch production process is not easy. The polyester resin may have an average particle size of 70% or more of 800 to 2000. mu.m, specifically 1000 to 2000. mu.m, more specifically 1200 to 2000. mu.m.
The masterbatch composition further contains a polyfunctional compound which is crosslinked with the foamable resin to increase the viscosity.
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. When the content of the polyfunctional compound is less than 1% by weight, the effect of increasing the viscosity of the foamed resin is insignificant, and when the content is more than 30% by weight, the processability of the master batch composition may be lowered.
Such polyfunctional compounds may be selected from the group consisting of Pyromellitic dianhydride (PMDA), benzophenone dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, bis (3, 4-dicarboxyphenyl) sulfide dianhydride, bisphenol a bisether dianhydride, 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 ', 3, 3' -biphenyltetracarboxylic dianhydride, hydroquinone bisether dianhydride, bis (3, 4-dicarboxyphenyl) sulfoxide dianhydride and 3,4,9, 10-perylenetetracarboxylic dianhydride. Specifically, pyromellitic dianhydride can be used as the polyfunctional compound in the present invention.
In this case, the melting point of the polyfunctional compound may be 270 ℃ or higher, specifically 270 to 350 ℃, 270 to 330 ℃, 270 to 310 ℃ or 270 to 290 ℃. For example, when the polyfunctional compound is Pyromellitic dianhydride (PMDA), the melting point may be 280 ± 5 ℃.
In addition, in order to improve processability and physical properties of the resin, the master batch composition of the present invention may further comprise conventionally known additives, for example, antioxidants, heat stabilizers, fillers, flame retardants, mold release agents, colorants and other materials. Specifically, a heat stabilizer may be used as an additive in the present invention.
The heat stabilizer is a 5-valent and/or 3-valent phosphorus compound, or may contain a phenol-based compound having a large steric hindrance in the chemical structure. Specifically, the 5-valent and/or 3-valent phosphorus compound may include trimethylphosphite, phosphoric acid, phosphorous acid, tris (2, 4-di-t-butylphenyl) phosphite, and the like. In addition, the large phenolic compound sterically hindered in chemical structure may include Pentaerythritol tetrakis 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate (Pentaerythritol tetrakis (3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, Irganox 1010), 1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane (1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane), octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate (octadecacyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate), N' -hexamethylenebis (3, 5-t-butyl-4-hydroxyhydrocinnamide) (N, N '-hexamethynebis (3,5-di-tert-butyl-4-hydroxyhydrocinnamamide)), ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] (ethylphenylebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate ], and N, N' - (Hexane-1,6-diyl) bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide (N, N '- (Hexane-1,6-diyl) bis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl)) acrylamide (N, N' - (Hexane-1,6-diyl) bis (3- (3, 5-di-tert-butyl-4-hydroxyhydrocinnamide)). furthermore, the content of the heat stabilizer may be 0.1 to 1% by weight based on the total weight of the masterbatch composition, but is not limited thereto.
The masterbatch composition may have a form such as a pellet (pellet), a granule (grain), a bead (bead), a chip (chip), or a powder (powder) form in some cases. The average size is not particularly limited, but in the case of pellet form, the length of the pellets may be 3 to 6mm for uniformity of the pores formed in the foam.
In another aspect, a method of making a masterbatch composition of an embodiment may include: a step of pulverizing a polyester resin having a melting point of 200 ℃ or lower; and a step of extruding and pelletizing the pulverized polyester resin and polyfunctional compound with an extruder.
The method of manufacturing a masterbatch composition of another embodiment may include: a step of pulverizing a polyester resin having a melting point of more than 200 ℃; and a step of extruding and pelletizing the pulverized polyester resin, polyolefin resin and polyfunctional compound with an extruder.
Here, the polyester resin, the polyolefin resin, and the polyfunctional compound are specifically described as above, and redundant description is omitted.
The step of pulverizing the polyester resin may be a step of pulverizing the polyester resin to an average particle size of 600 to 2000 μm. In this case, 70% or more of the polyester resin may have an average particle size of 800 to 2000. mu.m.
In the granulating step, the temperature in the granulating step may be 200 ℃ or lower, specifically 180 to 190 ℃.
Specifically, when a polyester resin having a melting point of 200 ℃ or lower is pulverized, the pelletizing step temperature is a temperature lower than the melting point of the polyfunctional compound as the domain of the master batch composition and higher than the melting point of the polyester resin as the matrix. Here, the pelletized polyfunctional compound as the microdomain in the master batch may be uniformly dispersed in the polyester resin as the matrix. In addition, the polyfunctional compound is not melted during pelletization, and the reaction between the polyester resin and the polyfunctional compound can be prevented, so that the polyfunctional compound can be prevented from being thermally decomposed.
On the other hand, when the polyester resin having a melting point of more than 200 ℃ is pulverized and pelletized further comprising a polyolefin resin, the temperature in the pelletization step is lower than the melting points of the polyester resin and the polyfunctional compound of the master batch composition and higher than the melting point of the polyolefin resin. Here, the polyester resin in the pelletized master batch can maintain the average particle size in the above-described pulverization step. In addition, the polyester resin and the polyfunctional compound are not melted in the pelletization process, and thus the reaction between the polyester resin and the polyfunctional compound can be prevented. Therefore, the polyfunctional compound can be prevented from being thermally decomposed.
As a result, thermal decomposition of the additive mixed into the resin melt can be prevented at the time of extrusion and foaming of the polyester resin. Therefore, there are advantages that the process stability is excellent and the expansion ratio of the produced foam sheet is excellent.
In addition, the present invention also provides a method for manufacturing a foamed sheet using the above-described masterbatch composition.
The method for manufacturing a foam sheet according to an embodiment may include: a step of mixing a master batch composition containing a polyester resin having a melting point of 200 ℃ or lower and a polyfunctional compound, a polyester resin having a melting point of 200 to 270 ℃, and inorganic particles containing an alkaline earth metal carbonate to produce a resin melt; a step of mixing a foaming agent into the resin melt to form a foamable melt; and a step of subjecting the foamable melt to extrusion foaming.
The method for producing a foam sheet according to another embodiment may include: a step of mixing a master batch composition, a polyester resin having a melting point of 200 to 270 ℃, and inorganic particles containing an alkaline earth metal carbonate to produce a resin melt, the master batch composition comprising a polyester resin having a melting point of more than 200 ℃, a polyolefin resin, and a polyfunctional compound; a step of mixing a foaming agent into the resin melt to form a foamable melt; and a step of producing a foamed sheet by extrusion foaming the foamable melt.
The step of producing the resin melt may be performed at a temperature of 260 to 300 ℃.
The resin melt may include 1 to 30 wt% of the masterbatch composition, 50 to 95 wt% of a polyester resin having a melting point of 200 to 270 ℃, and 1 to 30 wt% 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 weight of the entire resin melt. In this case, when the content of the master batch composition is less than 1% by weight, it is difficult to achieve a desired effect of increasing the viscosity of the foamed resin, and when it is more than 30% by weight, problems such as a decrease in processability may occur.
The polyester resin may be 1 or more selected from the group consisting of aromatic and aliphatic polyester resins synthesized from a dicarboxylic acid component and a diol component or hydroxycarboxylic acid. Examples of the polyester resin are as described above. The polyester resin may have a form such as a pellet (pellet), a granule (grain), a bead (bead), a chip (chip), or a powder (powder) form in some cases.
The resin melt containing the alkaline earth metal carbonate can reduce the size of pores of the foamed sheet, improve the density, and reduce the occurrence of wrinkles (corrugation) because the surface of the sheet is uniform, thereby exhibiting excellent thermoformability. Further, calcium carbonate is uniformly distributed in the polyester resin, and the thermal conductivity of the foamed sheet obtained by extrusion foaming of the resin is increased, so that the problem that the foamed sheet is broken at the time of molding the foamed sheet can be solved.
The alkaline earth metal carbonate may be an inorganic carbonate containing 1 or more cations selected from the group consisting of Ca, Mg, and Ba. In particular, the inorganic particles containing an alkaline earth metal carbonate may comprise calcium carbonate (CaCO)3) Magnesium carbonate (MgCO)3) And barium carbonate (BaCO)3) More specifically, the inorganic particles of the present invention may comprise calcium carbonate.
The inorganic particles may have an average size of 1.0 to 5.0 μm. For example, the inorganic carbonate may have an average particle size of 1.0 to 4.0. mu.m, 1.0 to 3.0. mu.m, 1.0 to 2.0. mu.m, 2.0 to 5.0. mu.m, or 3.0 to 5.0. mu.m.
The inorganic particles containing the alkaline earth metal carbonate may be produced in the form of a masterbatch by mixing the polyester resin and the masterbatch composition as a resin melt.
For example, the step of extrusion foaming may inject one or more additives selected from the group consisting of hydrophilizing agents, heat stabilizers, water repellents, cell size enlarging agents, infrared attenuating agents, plasticizers, fire-retardant chemicals, pigments, elastic polymers, extrusion aids, antioxidants, idle rotation preventing agents, and UV absorbers into the fluid connection line. Among additives required for the production of the foamed sheet, additives not fed into the fluid connection line may be fed into the extrusion step.
The water repellent is not particularly limited, and may include, for example, a mixture of silicon, epoxy, cyanoacrylate, polyvinyl acrylate, ethylene vinyl acetate, acrylic, chloroprene rubber, a mixed system of a polyurethane resin and a polyester resin, a mixed system of a polyol and a polyurethane resin, a mixed system of an acrylic fiber polymer and a polyurethane resin, a mixed system of a polyimide, a mixed system of a cyanoacrylate and a urethane, and the like.
As an example of the blowing agent, N may be used2、CO2Freon, butane, pentane, neopentane, hexane, isohexane, heptane, hexane, heptane,Physical blowing agents such as isoheptane and methyl chloride, specifically butane can be used in the present invention.
The step of extrusion foaming is carried out by cooling the foamable melt at 220 to 260 ℃ for easy foaming and then passing the cooled foamable melt through a Die (Die). In this case, the intrinsic viscosity of the expandable melt may be 0.9dL/g or more and 1.2dL/g to 1.5 dL/g. By controlling the intrinsic viscosity of the resin to be suitable for foaming, a foam having a high expansion ratio can be efficiently produced. In addition, the formed foam sheet may be maintained in shape using a Calibrator (Calibrator).
The average foaming density of the foamed sheet manufactured according to KS M ISO 845:2012 can be 100-600 kg/M3、100～500kg/m3、100～400kg/m3、100～300kg/m3、100～200kg/m3、200～600kg/m3、300～600kg/m3、400～600kg/m3Or 500 to 600kg/m3。
In addition, the average thickness of the foamed sheet may be in the range of 1.0 to 5.0 mm. For example, the average thickness of the foamed sheet may be 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 5.0mm, or 4.0 to 5.0 mm.
Hereinafter, the present invention will be described in detail by way of examples, but the following examples are merely illustrative of the present invention and the present invention is not limited to the following examples.
Production example 1
Polyethylene terephthalate (PET) having a melting point of 180 ℃ is dried at 130 ℃ to remove moisture, and pulverized to an average particle size of 600 to 2000 μm. In this case, 70% or more of the pulverized PET has an average particle size of 800 to 2000. mu.m. Thereafter, 89.9 wt% of the pulverized PET, 10 wt% of pyromellitic dianhydride (PMDA), and 0.1 wt% of a heat stabilizer (Irganox 1010) were mixed to prepare a composition, and the prepared composition was pelletized at 185 ℃ by an extruder to prepare a master batch.
Production examples 2 and 3
A master batch was produced by the same procedure as in production example 1, except that the melting point of PET was adjusted as shown in table 1 below.
Production example 4
Polyethylene terephthalate (PET) having a melting point of 250 ℃ is dried at 130 ℃ to remove moisture, and pulverized to an average particle size of 600 to 2000 μm. In this case, 70% or more of the pulverized PET particles have an average particle size of 800 to 2000 μm. Then, 60 wt% of the pulverized PET, 29.9 wt% of Linear Low Density Polyethylene (LLDPE), 10 wt% of pyromellitic dianhydride (PMDA), and 0.1 wt% of heat stabilizer (Irganox 1010) were mixed to prepare a composition, and the prepared composition was pelletized at 185 ℃ by an extruder to prepare a master batch.
Production examples 5 and 6 and comparative production example 1
A master batch was produced by the same procedure as in production example 4, except that the PET and LLDPE contents were adjusted as described in table 1 below.
Comparative production example 2
Instead of the pulverized PET used in production example 4, pulverized PET having an average particle size of 100 to 300 μm and an average particle size of 100 to 200 μm which is 80% or more of the pulverized PET was used. Thereafter, a master batch was produced by the same procedure as in production example 4, except that the contents of PET and LLDPE were adjusted as shown in table 1 below.
[ Table 1]
Figure BDA0003358839650000111
[ example 1]
To produce a polyester foamed sheet, first, 100 parts by weight of a polyethylene terephthalate (PET) resin was dried at 180 ℃ to remove moisture, 92.5% by weight of the moisture-removed PET resin, 4.5% by weight of the master batch composition produced in production example 1, and 3% by weight of calcium carbonate having an average particle size of 1.0 to 5.0 μm were mixed in an extruder, and the mixture was heated at 280 ℃ to produce a polyester foamed sheetA resin melt is produced. Thereafter, 1.5 parts by weight of butane as a blowing agent was charged into an extruder based on 100 parts by weight of the PET resin, and the resin melt was cooled to 250 ± 2 ℃. The cooled resin melt was extrusion-foamed while passing through a Die (Die) to produce a PET foamed sheet having an average thickness of 2.0 mm. At this time, the density of the produced PET foamed sheet was 350kg/m3。
[ examples 2 to 6]
Foamed sheets were produced by the same procedure as in example 1, except that the master batch compositions produced in production examples 2 to 6 were used instead of the master batch composition produced in production example 1.
Comparative examples 1 and 2
Foamed sheets were respectively produced by the same procedure as in example 1, except that the master batch compositions produced in comparative production examples 1 and 2 were respectively used instead of the master batch composition produced in production example 1.
[ Experimental example ]
The physical properties and processability at the time of production of the foamed sheets produced in examples 1 to 6 and comparative examples 1 and 2 were evaluated. Specifically, the physical properties and processability were measured in the following manner, and the results are shown in table 2 below.
1) Intrinsic Viscosity (IV) measurement
The foamed sheet was dissolved in a mixed solution of phenol/tetrachloroethane (mixing ratio: 50 wt%/50 wt%), to prepare a 0.5 wt% solution, and the viscosity of the solution at 35 ℃ was measured with an Ubbelohde viscometer.
2) Measurement of average thickness and expansion ratio of expanded sheet (Density measurement)
In order to measure the average thickness of each foamed sheet, the entire width of each foamed sheet was divided into 8 sections at regular intervals, and the average value was calculated after measuring the thickness with an indicator (ID-C112, MITutoyo Co.).
In order to measure the average foam density of each foam sheet, a sample was taken out of each foam sheet at a width of 2cm × a length of 2cm, and the foam density was measured with a water electronic densitometer (EW300SG, MIRAGE).
3) Evaluation of processability
The foam processability of the foam sheet was evaluated by selecting 2 or more samples at random among the produced foam sheets, measuring the density, and then evaluating the uniformity of the measured density. Specifically, 10 samples were randomly selected from 30 minutes after the start of production of the foamed sheet to the end of production, the density was measured in the same manner as in the above method, and the variation was derived based on the average value of the measured densities of the 10 samples.
4) Confirmation of foreign matter Generation level
The degree of generation of foreign matter in the die (die) and mandrel (mandrel) of the foaming device was visually confirmed.
[ Table 2]
Figure BDA0003358839650000131
As is clear from table 2, the master batch compositions of production examples 1 to 6 contain the polyester resin (PET) as a main component together with the polyfunctional compound (PMDA), and thus the polyester resin can be uniformly mixed with the polyester foamed resin during extrusion and foaming of the polyester resin, and it can be confirmed that the foamed sheets of examples 1 to 6 have higher intrinsic viscosity than those of comparative examples 1 and 2.
In addition, the foamed sheets of examples 1 to 6 showed low density variation relative to comparative example 1. This is because the thermal decomposition of the additive mixed in the resin melt is prevented during extrusion and foaming of the polyester resin, and it is confirmed that the process stability is excellent and the expansion ratio of the foamed sheet produced is excellent.
On the other hand, in examples 1 to 3, it was confirmed that no foreign matter was generated in the die and the mandrel of the foaming apparatus by using a low melting point polyester resin (PET) compatible with the foaming resin as the matrix of the master batch composition.
In the case of examples 4 to 6, the master batch composition contained a polyethylene resin (LLDPE) and a polyester resin (PET) as main components, so that the amount of foreign matter generated in the die and mandrel of the foaming apparatus was only small as compared with comparative examples 1 and 2.
In addition, in the case of comparative example 2, the foaming characteristics were exhibited at the same level as in the examples, but the average particle size of the polyester resin in the master batch was too small, which has a problem that handling in the master batch production process was not easy.
While the present invention has been described with reference to the preferred embodiments thereof, it is to be understood that various modifications and changes can be made by those skilled in the art or persons having ordinary knowledge in the art without departing from the spirit and scope of the present invention as set forth in the claims below.
Therefore, the technical scope of the present invention is not limited to the contents described in the detailed description of the specification, but must be determined based on the claims.
Industrial applicability
The master batch composition of the embodiment of the present invention includes the polyester resin as a main component together with the polyfunctional compound, so that the master batch composition can be uniformly mixed with the polyester foaming resin during extrusion and foaming of the polyester resin, and can remove generation of foreign substances. In addition, thermal decomposition of the additives mixed into the resin melt can be prevented at the time of extrusion and foaming of the polyester resin. Therefore, the process stability is excellent, and the expansion ratio of the produced foam sheet is excellent.

Claims (13)

1. A master batch composition comprising a carrier resin and 1 to 30% by weight of a polyfunctional compound,
and the carrier resin comprises 70-99 wt% of polyester resin with a melting point of 200 ℃ or below, or 55-85 wt% of polyester resin with a melting point of more than 200 ℃ and 10-40 wt% of polyolefin resin.
2. The masterbatch composition according to claim 1, wherein the carrier resin comprises 70 to 99 wt% of a polyester resin having a melting point of 200 ℃ or lower,
has a structure in which a polyfunctional compound is dispersed as domains in a matrix of a polyester resin.
3. The masterbatch composition of claim 1, wherein the polyester resin is Polyethylene Terephthalate (PET).
4. The master batch composition according to claim 3, wherein the polyethylene terephthalate is a polymer of an acid component comprising terephthalic acid and isophthalic acid and a diol component comprising 1 or more of ethylene glycol and diethylene glycol,
the content of isophthalic acid is 10 to 30 mol% based on 100 mol% of the acid component.
5. The masterbatch composition as claimed in claim 1, wherein the polyester resin has an average particle size of 600 μm to 2000 μm.
6. The masterbatch composition according to claim 5, wherein 70% or more of the polyester resin has an average particle size of 800 to 2000 μm.
7. The masterbatch composition of claim 1, wherein the polyolefin resin is Linear Low Density Polyethylene (LLDPE).
8. The master batch composition according to claim 1, wherein the polyfunctional compound is selected from the group consisting of pyromellitic dianhydride, benzophenone dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, bis (3, 4-dicarboxyphenyl) sulfide dianhydride, bisphenol A bisether dianhydride, 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 ', 3, 3' -biphenyltetracarboxylic dianhydride, hydroquinone bisether dianhydride, bis (3, 4-dicarboxyphenyl) sulfoxide dianhydride and 3,4,9, 10-perylenetetracarboxylic dianhydride.
9. The masterbatch composition of claim 1, wherein the masterbatch composition further comprises a thermal stabilizer.
10. A method for manufacturing a foamed sheet, wherein the manufacturing method comprises:
a step of mixing a master batch composition containing a carrier resin and 1 to 30 wt% of a polyfunctional compound, a polyester resin having a melting point of 200 to 270 ℃, and inorganic particles containing an alkaline earth metal carbonate to produce a resin melt; and
a step of subjecting the resin melt to extrusion foaming using an extruder,
and the carrier resin comprises 70-99 wt% of polyester resin with a melting point of 200 ℃ or below, or 55-85 wt% of polyester resin with a melting point of more than 200 ℃ and 10-40 wt% of polyolefin resin.
11. The method for producing a foam sheet according to claim 10, wherein the resin melt comprises 1 to 30 wt% of a master batch composition, 50 to 95 wt% of the polyester resin having a melting point of 200 to 270 ℃, and 1 to 30 wt% of the inorganic particles.
12. The method for producing a foamed sheet according to claim 10, wherein the alkaline earth metal element is 1 or more selected from the group consisting of Ca, Mg and Ba, and the inorganic particles have an average size of 1 to 5 μm.
13. A foamed sheet produced by the production method according to any one of claims 10 to 12,
average foam density of 100kg/M based on KS M ISO 845:20123～600kg/m3The average thickness is 1.0 mm-5.0 mm.
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