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WO2010062113A2 - Heat-expandable flame-retardant polyolefin resin composition and flame-retardant composite panel using the same - Google Patents

Heat-expandable flame-retardant polyolefin resin composition and flame-retardant composite panel using the same Download PDF

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Publication number
WO2010062113A2
WO2010062113A2 PCT/KR2009/006993 KR2009006993W WO2010062113A2 WO 2010062113 A2 WO2010062113 A2 WO 2010062113A2 KR 2009006993 W KR2009006993 W KR 2009006993W WO 2010062113 A2 WO2010062113 A2 WO 2010062113A2
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Prior art keywords
heat
retardant
polyolefin resin
flame
weight
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Ceased
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PCT/KR2009/006993
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French (fr)
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WO2010062113A3 (en
Inventor
Soon Jong Lee
Ki Su Kim
Won June Choi
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JINYOUNGTECH CO Ltd
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JINYOUNGTECH CO Ltd
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Publication of WO2010062113A2 publication Critical patent/WO2010062113A2/en
Publication of WO2010062113A3 publication Critical patent/WO2010062113A3/en
Anticipated expiration legal-status Critical
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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • 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
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • 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
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • 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
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • 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
    • C08J2203/22—Expandable microspheres, e.g. Expancel®
    • 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
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
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    • C08J2421/00—Characterised by the use of unspecified rubbers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • 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
    • 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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the present invention relates to a heat-expandable flame-retardant polyolefin resin composition and a flame-retardant composite panel using the same, and more particularly, to a heat-expandable flame-retardant polyolefin resin composition including a polyolefin resin, an inorganic flame retardant and a heat-expandable microcapsule, and a composite panel formed using the same.
  • an aluminum composite panel used as a constructional finishing material has a multi-layered structure in which aluminum, an adhesive layer, a support (a polyethylene resin), an adhesive and aluminum are sequentially formed.
  • the multi-layered structure is formed by providing a thin aluminum plate having a thickness of 0.5 mm or less, and adhering an inexpensive plastic material as a support to the aluminum plate to reduce the use of an expensive aluminum platter.
  • flowability of the material used as a support is important. If the flowability is not good, the material flow on the adhesive layer is non-uniform, and thus it is difficult to produce a continuous product due to an increase in extrusion load. When the flowability is excessively high, due to heat sagging occurring between an extrusion die and a polishing roll, a non-uniform bank is formed on the polishing roll, and thus deviations in thickness occur and the adhesive layer is non-uniformly applied.
  • the polyethylene resin used as a support for the conventional aluminum composite panel formed by such a method is light and inexpensive, and is used for various purposes due to its excellent properties. However, due to its high combustibility, its range of uses has been limited.
  • an inorganic flame-retardant for example, magnesium hydroxide and/or aluminum hydroxide, is mixed with a resin composition, thereby providing a sufficient flame-retardant property to a product formed of the resin composition including the inorganic flame-retardant.
  • a non-halogenated flame-retardant polyolefin resin composition including 15 to 35wt% of a polyolefin resin, 60 to 80wt% of an inorganic flame-retardant, and 0 to 15wt% of a lightweight filler is disclosed.
  • the above-mentioned composition has improved extrusion processibility, since it has a high content of the inorganic flame-retardant for maintaining the flame-retardant property, and a higher specific gravity than that of the polyethylene resin, for example, about 1.3 to 1.7, production costs of a flame-retardant aluminum composite panel formed using the composition are increased.
  • the present inventors found from continuous research on a method of forming a resin composition and an aluminum composite panel that an aluminum composite panel having a low specific gravity can be formed using the above-mentioned composition as a support by thermally expanding a heat-expandable microcapsule during extrusion to give a foaming effect, leading to completion of quasi-non-combustible to non-combustible composite panels having low specific gravities according to Korean Industrial Standards KS F5660-1.
  • the present invention is directed to a heat-expandable flame-retardant polyolefin resin composition and a heat-expandable composite panel using the same, which can reduce the specific gravity by foaming a heat-expandable microcapsule, make the panel lightweight and maintain a required level of a flame retardant property by reducing the amount of a flame-retardant to be used.
  • ease of handling and a reduction in production cost can be provided.
  • the present invention provides a heat-expandable flame-retardant polyolefin resin composition, including: 15 to 40 parts by weight of a polyolefin resin, 60 to 80 parts by weight of an inorganic flame retardant, and 0.2 to 5 parts by weight of a heat-expandable microcapsule.
  • the present invention provides a flame-retardant composite panel including the heat-expandable flame-retardant polyolefin resin composition.
  • the present invention provides a method of forming a flame-retardant composite panel, including: preparing a heat-expandable flame-retardant polyolefin resin composition by mixing 15 to 40 parts by weight of a polyolefin resin, 60 to 80 parts by weight of an inorganic flame retardant, and 0.2 to 5 parts by weight of a heat-expandable microcapsule based on the total weight of the resin composition; and foaming the heat-expandable flame-retardant polyolefin resin composition and adhering the foamed heat-expandable flame-retardant polyolefin resin composition to a metal plate.
  • the present invention relates to a heat-expandable flame-retardant polyolefin resin composition, which includes 15 to 40 parts by weight of a polyolefin resin, 60 to 80 parts by weight of an inorganic flame retardant, and 0.2 to 5 parts by weight of a heat-expandable microcapsule.
  • flame-retardant means flame-proof and flame-resistant.
  • the polyolefin resin according to the present invention is a mixture of a polyethylene resin and an ethylene copolymer, a mixture of a polyethylene resin and a thermoplastic rubber, or a combination thereof.
  • the content of the polyolefin resin may be 15 to 40 parts by weight per 100 parts by weight of the total heat-expandable flame-retardant polyolefin resin composition.
  • the amount of the polyolefin resin when the amount of the polyolefin resin is less than 15 parts by weight, it is difficult to perform an extrusion process due to an increase in content of the heat-expandable microcapsule, and when the amount of the polyolefin resin is more than 40 parts by weight, it may not meet a required level of quasi-non-combustibility according to KS F5660-1.
  • the polyethylene resin may be included in an amount of at least 20 to 80 parts by weight per 100 parts by weight of the total polyolefin resin, and other components such as an ethylene copolymer and/or thermoplastic rubber may be included in amounts corresponding to the remaining parts by weight.
  • the heat transformation temperature and flexural strength of the resin composition may be reduced, and when the content of the polyethylene resin is more than 80 parts by weight, flexibility is reduced, cracks may form during formation of a flexure, and heat sagging may occur during processing.
  • a support can have adhesion failure and thickness deviation due to a non-uniform bank.
  • the polyethylene resin may be a low-density polyethylene (LDPE) resin, a very-low-density polyethylene (VLDPE) resin, a linear low-density polyethylene (LLDPE) resin or a combination thereof, and may be included in an amount of 20 to 80 parts by weight per 100 parts by weight of the total polyolefin resin.
  • the density of the polyethylene resin may be in the range of 0.89 to 0.929 g/cm 3
  • the melt index thereof may be in the range of 10 to 60 g per 10 minutes.
  • melt index when the melt index is less than 10 g per 10 minutes, extrusion moldability may be degraded, and when the melt index is more than 60 g per 10 minutes,heat sagging may occur and thus a the non-uniform bank may be formed.
  • the ethylene copolymer includes at least one selected from an ethylene-propylene copolymer, an ethylene-octene copolymer, an ethylene-butene copolymer, an ethylene-hexene copolymer, ethylene vinylacetate, ethylene ethylacrylate, and ethylene methylacrylate.
  • the polyethylene resin is included in an amount of 20 to 80 parts by weight per 100 parts by weight of the total polyolefin resin, and the ethylene copolymer may be included in an amount corresponding to the remaining parts by weight.
  • the thermoplastic rubber may be at least one selected from dynamic vulcanization products prepared by reaction of the polyolefin resins such as a styrene-butadiene-styrene (SBS) copolymer and a styrene-isoprene-styrene (SIS) copolymer with their hydrogenated products such as a styrene-ethylene-butylene-styrene (SEBS) copolymer and a styrene-ethylene-propylene-styrene (SEPS) copolymer, hydrogenated styrene-butadiene rubber (HSBR), and an ethylene-propylene-diene monomer (EPDM).
  • the polyethylene resin is included in an amount of 20 to 80 parts by weight of 100 parts by weight per the total polyolefin resin, and an amount of the thermoplastic rubber to be included may be the remaining parts by weight.
  • the inorganic flame retardant according to the present invention may be included in an amount of 60 to 80 parts by weight, and preferably 65 to 75 parts by weight, per 100 parts by weight of the total resin composition.
  • any one generally known to those skilled in the art can be used, which may be magnesium hydroxide, aluminum hydroxide, magnesium carbonate, or a mixture thereof.
  • the inorganic flame retardant may have a particle size of 1 to 60 m, and a BET surface area of 0.4 to 35 m 2 /g.
  • the flame-retardant property may be reduced, for example, to below the quasi-non-combustibility level according to KS F5660-1.
  • the content of the inorganic flame retardant is more than 80 parts by weight, processibility may be degraded due to an increase in extrusion load, the bank may be non-uniform during heat expansion, and thus it can be difficult to form a final product.
  • the heat-expandable microcapsule according to the present invention is included in the resin composition to reduce the specific gravity when it expands by heat application and thus foams.
  • the heat-expandable microcapsule may be any one known in the art, but is preferably liquid hydrocarbon in a polymer shell with a size of 3 to 50 m and formed of a nitrile-based copolymer.
  • the nitrile-based copolymer may be at least one selected from the group consisting of an acrylonitrile copolymer, a methacrylonitrile copolymer, an alpha-chloroacrylonitrile copolymer, an alpha-ethoxyacrylonitrile copolymer, and a fumaronitrile copolymer.
  • the expansion initiation temperature of the heat-expandable microcapsule according to the present invention may be equal to or higher than the melting point of the polyolefin resin, and the maximum expansion temperature of the heat-expandable microcapsule may be 150 to 220 °C.
  • the expansion initiation temperature of the heat-expandable microcapsule may be equal to or higher than the melting point of the polyolefin resin. Since polyolefin resins have various melting points according to the kind thereof, the heat-expandable microcapsule also has various expansion initiation temperatures according to the polyolefin resins to be used herein, which is preferably in the range of 90 to 120 °C. When the expansion initiation temperature is lower than the melting point of the polyolefin resin, the heat-expandable microcapsule may pre-expand, and thus it is difficult to obtain the composition according to the present invention.
  • the maximum expansion temperature refers to a temperature at which the heat-expandable microcapsule stays for 2 minutes in an extruder until fully expanded.
  • the maximum expansion temperature of the heat-expandable microcapsule may be 150 to 220 °C.
  • the maximum expansion temperature is less than 150 °C, because of the possibility of pre-expansion of the heat-expandable microcapsule during preparation of the polyolefin resin composition of the present invention, a roll-mixing time to mix the polyolefin resin composition in a roll-mixing machine is shortened, and thus it is difficult to obtain a uniform mixture. Even if a uniform polyolefin resin composition is obtained, it pre-expands and thus is shrunken upon passing through the extruder, which extrudes the polyolefin resin composition, and thus obtaining a foamy effect is difficult.
  • the microcapsule When the heat-expandable microcapsule stays for too long in the roll-mixing machine or extruder at the maximum expansion temperature, the microcapsule may be shrunken due to transmission loss of gas, thereby degrading the foamy effect.
  • pre-expansion in the roll-mixing machine should be avoided.
  • the content of the heat-expandable microcapsule according to the present invention may be 0.2 to 5 parts by weight, and preferably, 0.5 to 3 parts by weight per 100 parts by weight of the total resin composition.
  • the specific gravity When the content of the microcapsule is less than 0.2 parts by weight, the specific gravity is decreased less. When the content of the microcapsule is more than 5 parts by weight, the decrease in specific gravity may be insignificant, and thus it is difficult to form a bank on the polishing roll, thereby having adhesion failure and thickness deviation during formation of a composite panel, specifically, an aluminum composite panel.
  • the heat-expandable flame-retardant polyolefin resin composition may further include an antioxidant, a process aid, an organic/inorganic foaming agent, a filler dispersing agent, and/or a dehumidifying agent, and its content is not particularly limited, but may be small.
  • the present invention also relates to a flame-retardant composite panel including the heat-expandable flame-retardant polyolefin resin composition.
  • the composite panel is formed by sequentially stacking a metal plate, an adhesive layer, a polyolefin resin composition, an adhesive layer, and a metal plate.
  • the metal plate may be formed of aluminum, zinc, titanium or an alloy of at least two thereof.
  • the adhesive used for the adhesive layer may be a hot melt adhesive including, but not particularly limited to, ethylene vinyl acetate, polyester, polyethylene, polyurethane, polypropylene, SIS, polyamide, or a resin formed by mixing at least two thereof.
  • the present invention also relates to a method of forming a flame-retardant composite panel, including: preparing a heat-expandable flame-retardant polyolefin resin composition by mixing 15 to 40 parts by weight of a polyolefin resin, 60 to 80 parts by weight of an inorganic flame retardant, and 0.2 to 5 parts by weight of a heat-expandable microcapsule based on the total weight of the resin composition; and foaming the heat-expandable flame-retardant polyolefin resin composition and adhering it to a metal plate.
  • a polyolefin resin, an inorganic flame retardant and a heat-expandable microcapsule are mixed with each other by any method, which is not particularly limited, but is preferably by melt-mixing.
  • the heat-expandable flame-retardant polyolefin resin composition may include 15 to 40 parts by weight of the polyolefin resin, 60 to 80 parts by weight of the inorganic flame retardant, and 0.2 to 5 parts by weight of the heat-expandable microcapsule based on the total weight of the resin composition.
  • the heat-expandable flame-retardant polyolefin resin composition may be prepared using a mixing machine, and preferably a roll-mixing machine.
  • Examples of the roll-mixing machine may include, but are not particularly limited to, a twin screw extruder, a buss kneader, a continuous mixer, a banbury mixer, and a kneader.
  • the banbury mixer or the kneader is preferably used.
  • the roll-mixing machine may be maintained at 90 to 150 °C.
  • the step of preparing the heat-expandable flame-retardant polyolefin resin composition includes mixing 15 to 40 parts by weight of the polyolefin resin with 60 to 80 parts by weight of the inorganic flame retardant based on the total weight of the resin composition at 90 to 120 °C; and adding 0.2 to 5 parts by weight of the heat-expandable microcapsule to the mixture of the polyolefin resin and the inorganic flame retardant to be mixed together at 120 to 150 °C.
  • the mixing step is to mix the polyolefin resin with the inorganic flame-retardant by any method, which is not particularly limited, but is preferably by melt-mixing.
  • the mixture may include 15 to 40 parts by weight of the polyolefin resin and 60 to 80 parts by weight of the inorganic flame retardant based on the total weight of the resin composition.
  • the mixture may be prepared using a mixing machine, and preferably a roll-mixing machine.
  • the roll-mixing machine may be maintained at 90 to 120 °C.
  • the step of preparing the heat-expandable flame-retardant polyolefin resin composition also includes adding the heat-expandable microcapsule to the mixture prepared in the previous mixing step, particularly, the mixture formed by melt-mixing the polyolefin resin with the inorganic flame retardant.
  • the content of the inorganic flame retardant may be 0.2 to 5 parts by weight.
  • the addition of the heat-expandable microcapsule to the mixture of the polyolefin resin and the inorganic flame retardant may be performed at 90 to 120 °C.
  • the heat-expandable microcapsule is added to and mixed with, the mixture of the polyolefin resin and the inorganic flame retardant at 120 to 150 °C.
  • the mixing of the polyolefin resin composition may be performed in the roll-mixing machine, and at this time, pre-foaming should be avoided.
  • the roll-mixed heat-expandable flame-retardant polyolefin resin composition is foamed, and adhered to a metal plate.
  • the formation of the flame-retardant composite panel may be performed in the range of 150 to 220 °C.
  • Any apparatus for foaming the heat-expandable flame-retardant polyolefin resin composition known in the art may be used, and is preferably, though not particularly limited to, a T-die or single-screw extruder.
  • the single-screw extruder may have an L/D (the length of the extruder cylinder/the cylinder diameter) of 8 to 24, and the compression ratio of the screw is 1.1:1 to 2.5:1.
  • a refrigerant may be circulated in the screw.
  • the T-die according to the present invention When the T-die according to the present invention is used, three-layered co-extrusion is performed, that is, the polyolefin resin composition according to the present invention is extruded into a middle layer, and the adhesive resin is extruded into either of the above and underlying layers of the middle layer.
  • the foamed resin composition is provided to a roll, and adhered to a metal plate.
  • the roll used herein is any one generally used in the art, and preferably a calender roll.
  • the foamed resin composition is provided to the roll and adhered to the metal plates which are also provided along with the composition and thus are disposed on and under the roll, thereby completing the flame-retardant composite panel having a low specific gravity.
  • the metal plate may be formed of aluminum, zinc, titanium or an alloy of at least two thereof, and is preferably aluminum.
  • a composition sample obtained by roll-mixing components using a kneader was taken to measure the specific gravity prior to provision to an extruder, and expanded (foamed) through the extruder.
  • the specific gravity of the expanding sample used as a support was measured, and compared with the specific gravity of the sample.
  • the sample was compared with a flame-retardant composition without a microcapsule in Comparative Example 1, which has a specific gravity of 1.57, by examination with the naked eye.
  • the composition was roll-mixed using the kneader, and extruded so as to foam using an apparatus for forming a composite panel operated in a co-extrusion type, thereby completing a flame-retardant composite panel having a low specific gravity.
  • foam uniformity and bank uniformity on a calender roll were examined.
  • the thickness of an aluminum plate was 4 mm, the thickness of an alloy of each of the layers disposed on and under the plate was 0.5 mm, and the thickness of a support including an adhesive layer was 3 mm.
  • a sample was manufactured using the aluminum composite panel formed above, and evaluated for flame-retardant property.
  • the sample After the sample is irradiated with 50 kW/m 2 of radiation, it should have a total amount of heat generated for 10 minutes of 8 MJ/m 2 or less, and the maximum amount of heat emitted during the 10 minutes should not exceed 200 kW/m 2 for 10 seconds or longer, and there should be no hole in the sample after the 10-minute heating.
  • the composition passed through a 180-mm single screw extruder with a T-die [Fine Mechatronics Co. Ltd., Korea] to expand (foam), and it was then provided to a calender roll, where aluminum panels were adhered on and under the extruded composition, thereby forming an aluminum composite panel at a rate of 2.4 meter per minute.
  • the composition had a specific gravity of 1.58 prior to foaming, and pre-foaming was not observed.
  • a support for the aluminum composite panel which was obtained by foaming the composition, had a dramatic decrease in specific gravity to 1.16.
  • the oxygen index was 54, and thus the flame-retardant property satisfied the quasi-non-combustibility standard according to KS F5660-1. During extrusion, good foam uniformity and bank formation were observed. The results are shown in Table 2.
  • Example 1 A process was performed in the same manner as in Example 1, except that 1 part by weight of the heat-expandable microcapsule was added while the ratio of the polyethylene resin to the inorganic flame retardant was the same as in Example 1 (see Table 1).
  • the specific gravity of the composition was 1.57 prior to the foaming, and pre-foaming was not observed.
  • the specific gravity of the support was 0.96, which was similar to that of the polyethylene resin, and the oxygen index was 52.5, which means that the flame-retardant property satisfied the quasi-non-combustibility standard according to KS F5660-1. Good foam uniformity and bank formation were observed. The results are shown in Table 2.
  • Example 1 A process was performed in the same manner as in Example 1, except that 3 parts by weight of the heat-expandable microcapsule was added while the ratio of the polyethylene resin to the inorganic flame retardant was the same as in Example 1 (see Table 1).
  • the specific gravity of the composition was 1.55 prior to the foaming, and pre-foaming was not observed.
  • the specific gravity of the support was 0.84, which was lower than that of the polyethylene resin.
  • the oxygen index was 52, which means that the flame-retardant property satisfied the quasi-non-combustibility standard.
  • the foam uniformity was slightly decreased, and the bank formation was also slightly non-uniform, which did not cause any major problems in the formation of the product. The results are shown in Table 2.
  • Example 1 A process was performed in the same manner as in Example 1, except that the heat-expandable microcapsule was not added (see Table 1).
  • the specific gravity of the support for the aluminum composite panel was 1.58, which was significantly higher than that of the polyethylene resin (e.g., 0.924).
  • the oxygen index was 54, which means that the flame-retardant property satisfied the quasi-non-combustibility standard according to KS F5660-1.
  • good bank formation was observed on the calender roll. The results are shown in Table 2.
  • Example 1 A process was performed in the same manner as in Example 1, except that 6 parts by weight of the heat-expandable microcapsule was added while the ratio of the polyethylene resin to the inorganic flame retardant was the same as in Example 1 (see Table 1).
  • LLDPE has a MI of 20, and a specific gravity of 0.924 [JL210, SK Energy Co., Korea], 1) metallocene polyolefin resin was Engage 8200, commercially available from Dow Chemical in the U.S., 2) magnesium hydroxide was DG-800, commercially available from International Powder Engineering Co. in China, and 3) heat-expandable microcapsule was MSH-500, commercially available from Matsumotousiseiyaku, Co., Ltd. in Japan.
  • the specific gravity when the composition was foamed by adding the heat-expandable microcapsule, compared with when no heat-expandable microcapsule was added, the specific gravity was significantly reduced, and there was almost no adverse effect on the flame-retardant property.
  • the specific gravity can be similar to or lower than the polyethylene resin.
  • a heat-expandable microcapsule is foamed to reduce the specific gravity, and an amount of a flame-retardant resin composition to be used per volume is reduced to make a panel lightweight and maintain a flame-retardant property, which leads to ease of handling and a reduction in production cost.

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Abstract

Provided are a heat-expandable flame-retardant polyolefin resin composition including 15 to 40 parts by weight of a polyolefin resin, 60 to 80 parts by weight of an inorganic flame retardant, and 0.2 to 5 parts by weight of a heat-expandable microcapsule, and a flame-retardant composite panel using the same. The flame-retardant composite panel formed using the composition ensures a required flame-retardant property and is lightweight.

Description

HEAT-EXPANDABLE FLAME-RETARDANT POLYOLEFIN RESIN COMPOSITION AND FLAME-RETARDANT COMPOSITE PANEL USING THE SAME
The present invention relates to a heat-expandable flame-retardant polyolefin resin composition and a flame-retardant composite panel using the same, and more particularly, to a heat-expandable flame-retardant polyolefin resin composition including a polyolefin resin, an inorganic flame retardant and a heat-expandable microcapsule, and a composite panel formed using the same.
Generally, an aluminum composite panel used as a constructional finishing material has a multi-layered structure in which aluminum, an adhesive layer, a support (a polyethylene resin), an adhesive and aluminum are sequentially formed. The multi-layered structure is formed by providing a thin aluminum plate having a thickness of 0.5 mm or less, and adhering an inexpensive plastic material as a support to the aluminum plate to reduce the use of an expensive aluminum platter.
To form such an aluminum composite panel, in Japanese Laid-Open Patents Nos. Heisei 2-63734 and Heisei 2-63735, a method of forming an aluminum composite panel by continuous extrusion of a polyethylene resin used as a support is disclosed. However, the above method of forming the aluminum composite panel was amended to a method of co-extruding a polyethylene resin, which is a support, with an adhesive resin constituting an adhesive layer.
Here, for the co-extrusion, flowability of the material used as a support is important. If the flowability is not good, the material flow on the adhesive layer is non-uniform, and thus it is difficult to produce a continuous product due to an increase in extrusion load. When the flowability is excessively high, due to heat sagging occurring between an extrusion die and a polishing roll, a non-uniform bank is formed on the polishing roll, and thus deviations in thickness occur and the adhesive layer is non-uniformly applied.
The polyethylene resin used as a support for the conventional aluminum composite panel formed by such a method is light and inexpensive, and is used for various purposes due to its excellent properties. However, due to its high combustibility, its range of uses has been limited.
To overcome this problem, an inorganic flame-retardant, for example, magnesium hydroxide and/or aluminum hydroxide, is mixed with a resin composition, thereby providing a sufficient flame-retardant property to a product formed of the resin composition including the inorganic flame-retardant.
For example, in Korean Patent No. 10-0680822, a non-halogenated flame-retardant polyolefin resin composition including 15 to 35wt% of a polyolefin resin, 60 to 80wt% of an inorganic flame-retardant, and 0 to 15wt% of a lightweight filler is disclosed.
Though the above-mentioned composition has improved extrusion processibility, since it has a high content of the inorganic flame-retardant for maintaining the flame-retardant property, and a higher specific gravity than that of the polyethylene resin, for example, about 1.3 to 1.7, production costs of a flame-retardant aluminum composite panel formed using the composition are increased.
To overcome the above-mentioned problems, the present inventors found from continuous research on a method of forming a resin composition and an aluminum composite panel that an aluminum composite panel having a low specific gravity can be formed using the above-mentioned composition as a support by thermally expanding a heat-expandable microcapsule during extrusion to give a foaming effect, leading to completion of quasi-non-combustible to non-combustible composite panels having low specific gravities according to Korean Industrial Standards KS F5660-1.
The present invention is directed to a heat-expandable flame-retardant polyolefin resin composition and a heat-expandable composite panel using the same, which can reduce the specific gravity by foaming a heat-expandable microcapsule, make the panel lightweight and maintain a required level of a flame retardant property by reducing the amount of a flame-retardant to be used. Thus, ease of handling and a reduction in production cost can be provided.
In one aspect, the present invention provides a heat-expandable flame-retardant polyolefin resin composition, including: 15 to 40 parts by weight of a polyolefin resin, 60 to 80 parts by weight of an inorganic flame retardant, and 0.2 to 5 parts by weight of a heat-expandable microcapsule.
In another aspect, the present invention provides a flame-retardant composite panel including the heat-expandable flame-retardant polyolefin resin composition.
In still another aspect, the present invention provides a method of forming a flame-retardant composite panel, including: preparing a heat-expandable flame-retardant polyolefin resin composition by mixing 15 to 40 parts by weight of a polyolefin resin, 60 to 80 parts by weight of an inorganic flame retardant, and 0.2 to 5 parts by weight of a heat-expandable microcapsule based on the total weight of the resin composition; and foaming the heat-expandable flame-retardant polyolefin resin composition and adhering the foamed heat-expandable flame-retardant polyolefin resin composition to a metal plate.
Reference will now be made in detail to the present embodiments of the present invention, examples of which are shown in the accompanying drawings.
The present invention relates to a heat-expandable flame-retardant polyolefin resin composition, which includes 15 to 40 parts by weight of a polyolefin resin, 60 to 80 parts by weight of an inorganic flame retardant, and 0.2 to 5 parts by weight of a heat-expandable microcapsule.
Herein, the term flame-retardant means flame-proof and flame-resistant.
The polyolefin resin according to the present invention is a mixture of a polyethylene resin and an ethylene copolymer, a mixture of a polyethylene resin and a thermoplastic rubber, or a combination thereof. The content of the polyolefin resin may be 15 to 40 parts by weight per 100 parts by weight of the total heat-expandable flame-retardant polyolefin resin composition.
Here, when the amount of the polyolefin resin is less than 15 parts by weight, it is difficult to perform an extrusion process due to an increase in content of the heat-expandable microcapsule, and when the amount of the polyolefin resin is more than 40 parts by weight, it may not meet a required level of quasi-non-combustibility according to KS F5660-1.
Therefore, to prepare the polyolefin resin according to the present invention, the polyethylene resin may be included in an amount of at least 20 to 80 parts by weight per 100 parts by weight of the total polyolefin resin, and other components such as an ethylene copolymer and/or thermoplastic rubber may be included in amounts corresponding to the remaining parts by weight.
Here, when the content of the polyethylene resin is less than 20 parts by weight, the heat transformation temperature and flexural strength of the resin composition may be reduced, and when the content of the polyethylene resin is more than 80 parts by weight, flexibility is reduced, cracks may form during formation of a flexure, and heat sagging may occur during processing. Thus, a support can have adhesion failure and thickness deviation due to a non-uniform bank.
The polyethylene resin may be a low-density polyethylene (LDPE) resin, a very-low-density polyethylene (VLDPE) resin, a linear low-density polyethylene (LLDPE) resin or a combination thereof, and may be included in an amount of 20 to 80 parts by weight per 100 parts by weight of the total polyolefin resin. Here, the density of the polyethylene resin may be in the range of 0.89 to 0.929 g/cm3, and the melt index thereof may be in the range of 10 to 60 g per 10 minutes.
Here, when the melt index is less than 10 g per 10 minutes, extrusion moldability may be degraded, and when the melt index is more than 60 g per 10 minutes,heat sagging may occur and thus a the non-uniform bank may be formed.
The ethylene copolymer includes at least one selected from an ethylene-propylene copolymer, an ethylene-octene copolymer, an ethylene-butene copolymer, an ethylene-hexene copolymer, ethylene vinylacetate, ethylene ethylacrylate, and ethylene methylacrylate. The polyethylene resin is included in an amount of 20 to 80 parts by weight per 100 parts by weight of the total polyolefin resin, and the ethylene copolymer may be included in an amount corresponding to the remaining parts by weight.
The thermoplastic rubber may be at least one selected from dynamic vulcanization products prepared by reaction of the polyolefin resins such as a styrene-butadiene-styrene (SBS) copolymer and a styrene-isoprene-styrene (SIS) copolymer with their hydrogenated products such as a styrene-ethylene-butylene-styrene (SEBS) copolymer and a styrene-ethylene-propylene-styrene (SEPS) copolymer, hydrogenated styrene-butadiene rubber (HSBR), and an ethylene-propylene-diene monomer (EPDM). The polyethylene resin is included in an amount of 20 to 80 parts by weight of 100 parts by weight per the total polyolefin resin, and an amount of the thermoplastic rubber to be included may be the remaining parts by weight.
The inorganic flame retardant according to the present invention may be included in an amount of 60 to 80 parts by weight, and preferably 65 to 75 parts by weight, per 100 parts by weight of the total resin composition. As an available flame-retardant, any one generally known to those skilled in the art can be used, which may be magnesium hydroxide, aluminum hydroxide, magnesium carbonate, or a mixture thereof. Here, the inorganic flame retardant may have a particle size of 1 to 60 m, and a BET surface area of 0.4 to 35 m2/g.
Here, when the content of the inorganic flame retardant is less than 60 parts by weight, the flame-retardant property may be reduced, for example, to below the quasi-non-combustibility level according to KS F5660-1. When the content of the inorganic flame retardant is more than 80 parts by weight, processibility may be degraded due to an increase in extrusion load, the bank may be non-uniform during heat expansion, and thus it can be difficult to form a final product.
The heat-expandable microcapsule according to the present invention is included in the resin composition to reduce the specific gravity when it expands by heat application and thus foams. For the above-mentioned purpose, the heat-expandable microcapsule may be any one known in the art, but is preferably liquid hydrocarbon in a polymer shell with a size of 3 to 50 m and formed of a nitrile-based copolymer.
The nitrile-based copolymer may be at least one selected from the group consisting of an acrylonitrile copolymer, a methacrylonitrile copolymer, an alpha-chloroacrylonitrile copolymer, an alpha-ethoxyacrylonitrile copolymer, and a fumaronitrile copolymer.
The expansion initiation temperature of the heat-expandable microcapsule according to the present invention may be equal to or higher than the melting point of the polyolefin resin, and the maximum expansion temperature of the heat-expandable microcapsule may be 150 to 220 ℃.
Here, the expansion initiation temperature of the heat-expandable microcapsule may be equal to or higher than the melting point of the polyolefin resin. Since polyolefin resins have various melting points according to the kind thereof, the heat-expandable microcapsule also has various expansion initiation temperatures according to the polyolefin resins to be used herein, which is preferably in the range of 90 to 120 ℃. When the expansion initiation temperature is lower than the melting point of the polyolefin resin, the heat-expandable microcapsule may pre-expand, and thus it is difficult to obtain the composition according to the present invention.
The maximum expansion temperature refers to a temperature at which the heat-expandable microcapsule stays for 2 minutes in an extruder until fully expanded. The maximum expansion temperature of the heat-expandable microcapsule may be 150 to 220 ℃. When the maximum expansion temperature is less than 150 ℃, because of the possibility of pre-expansion of the heat-expandable microcapsule during preparation of the polyolefin resin composition of the present invention, a roll-mixing time to mix the polyolefin resin composition in a roll-mixing machine is shortened, and thus it is difficult to obtain a uniform mixture. Even if a uniform polyolefin resin composition is obtained, it pre-expands and thus is shrunken upon passing through the extruder, which extrudes the polyolefin resin composition, and thus obtaining a foamy effect is difficult.
When the heat-expandable microcapsule stays for too long in the roll-mixing machine or extruder at the maximum expansion temperature, the microcapsule may be shrunken due to transmission loss of gas, thereby degrading the foamy effect. To obtain the heat-expandable flame-retardant polyolefin composition of the present invention, pre-expansion in the roll-mixing machine should be avoided.
The content of the heat-expandable microcapsule according to the present invention may be 0.2 to 5 parts by weight, and preferably, 0.5 to 3 parts by weight per 100 parts by weight of the total resin composition.
When the content of the microcapsule is less than 0.2 parts by weight, the specific gravity is decreased less. When the content of the microcapsule is more than 5 parts by weight, the decrease in specific gravity may be insignificant, and thus it is difficult to form a bank on the polishing roll, thereby having adhesion failure and thickness deviation during formation of a composite panel, specifically, an aluminum composite panel.
Meanwhile, the heat-expandable flame-retardant polyolefin resin composition may further include an antioxidant, a process aid, an organic/inorganic foaming agent, a filler dispersing agent, and/or a dehumidifying agent, and its content is not particularly limited, but may be small.
The present invention also relates to a flame-retardant composite panel including the heat-expandable flame-retardant polyolefin resin composition.
The composite panel is formed by sequentially stacking a metal plate, an adhesive layer, a polyolefin resin composition, an adhesive layer, and a metal plate.
Here, the metal plate may be formed of aluminum, zinc, titanium or an alloy of at least two thereof.
The adhesive used for the adhesive layer may be a hot melt adhesive including, but not particularly limited to, ethylene vinyl acetate, polyester, polyethylene, polyurethane, polypropylene, SIS, polyamide, or a resin formed by mixing at least two thereof.
The present invention also relates to a method of forming a flame-retardant composite panel, including: preparing a heat-expandable flame-retardant polyolefin resin composition by mixing 15 to 40 parts by weight of a polyolefin resin, 60 to 80 parts by weight of an inorganic flame retardant, and 0.2 to 5 parts by weight of a heat-expandable microcapsule based on the total weight of the resin composition; and foaming the heat-expandable flame-retardant polyolefin resin composition and adhering it to a metal plate.
In the step of preparing the heat-expandable flame-retardant polyolefin resin composition, a polyolefin resin, an inorganic flame retardant and a heat-expandable microcapsule are mixed with each other by any method, which is not particularly limited, but is preferably by melt-mixing.
Here, the heat-expandable flame-retardant polyolefin resin composition may include 15 to 40 parts by weight of the polyolefin resin, 60 to 80 parts by weight of the inorganic flame retardant, and 0.2 to 5 parts by weight of the heat-expandable microcapsule based on the total weight of the resin composition.
In addition, the heat-expandable flame-retardant polyolefin resin composition may be prepared using a mixing machine, and preferably a roll-mixing machine.
Examples of the roll-mixing machine may include, but are not particularly limited to, a twin screw extruder, a buss kneader, a continuous mixer, a banbury mixer, and a kneader. Among said roll-mixing machines, the banbury mixer or the kneader is preferably used.
The roll-mixing machine may be maintained at 90 to 150 ℃.
Preferably, the step of preparing the heat-expandable flame-retardant polyolefin resin composition includes mixing 15 to 40 parts by weight of the polyolefin resin with 60 to 80 parts by weight of the inorganic flame retardant based on the total weight of the resin composition at 90 to 120 ℃; and adding 0.2 to 5 parts by weight of the heat-expandable microcapsule to the mixture of the polyolefin resin and the inorganic flame retardant to be mixed together at 120 to 150 ℃.
The mixing step is to mix the polyolefin resin with the inorganic flame-retardant by any method, which is not particularly limited, but is preferably by melt-mixing.
Here, the mixture may include 15 to 40 parts by weight of the polyolefin resin and 60 to 80 parts by weight of the inorganic flame retardant based on the total weight of the resin composition.
Moreover, the mixture may be prepared using a mixing machine, and preferably a roll-mixing machine. Here, the roll-mixing machine may be maintained at 90 to 120 ℃.
The step of preparing the heat-expandable flame-retardant polyolefin resin composition also includes adding the heat-expandable microcapsule to the mixture prepared in the previous mixing step, particularly, the mixture formed by melt-mixing the polyolefin resin with the inorganic flame retardant.
Here, the content of the inorganic flame retardant may be 0.2 to 5 parts by weight.
The addition of the heat-expandable microcapsule to the mixture of the polyolefin resin and the inorganic flame retardant may be performed at 90 to 120 ℃. The heat-expandable microcapsule is added to and mixed with, the mixture of the polyolefin resin and the inorganic flame retardant at 120 to 150 ℃.
The mixing of the polyolefin resin composition may be performed in the roll-mixing machine, and at this time, pre-foaming should be avoided.
In the step of forming the flame-retardant composite panel according to the present invention, the roll-mixed heat-expandable flame-retardant polyolefin resin composition is foamed, and adhered to a metal plate.
The formation of the flame-retardant composite panel may be performed in the range of 150 to 220 ℃.
Any apparatus for foaming the heat-expandable flame-retardant polyolefin resin composition known in the art may be used, and is preferably, though not particularly limited to, a T-die or single-screw extruder.
Here, the single-screw extruder may have an L/D (the length of the extruder cylinder/the cylinder diameter) of 8 to 24, and the compression ratio of the screw is 1.1:1 to 2.5:1.
When the L/D is less than 8, and the compression ratio of the screw is less than 1.1:1, an extruded amount may become non-uniform, and when the L/D is more than 24, the process time is longer and thus the composition has a high chance of being pre-foamed. Alternatively, when the compression ratio of the screw is more than 2.5:1, it is difficult to adjust the temperature due to heat generated by increasing an extrusion load and a shearing force, and thus it can be difficult to form a support for a uniformly-foamed composite panel.
To reduce the heat generated in the extruder as much as possible, a refrigerant may be circulated in the screw.
When the T-die according to the present invention is used, three-layered co-extrusion is performed, that is, the polyolefin resin composition according to the present invention is extruded into a middle layer, and the adhesive resin is extruded into either of the above and underlying layers of the middle layer.
The foamed resin composition is provided to a roll, and adhered to a metal plate. The roll used herein is any one generally used in the art, and preferably a calender roll.
Here, the foamed resin composition is provided to the roll and adhered to the metal plates which are also provided along with the composition and thus are disposed on and under the roll, thereby completing the flame-retardant composite panel having a low specific gravity.
The metal plate may be formed of aluminum, zinc, titanium or an alloy of at least two thereof, and is preferably aluminum.
Hereinafter, the present invention will be described in further detail with reference to the following examples. However, the examples are merely provided to describe the present invention in detail, not to limit the scope of the present invention.
Prior to explanation of the examples according to the present invention, a method of measuring properties of a material to be prepared according to the following example will be described.
[Method of Measuring Properties]
Specific Gravity: ASTM D1505
A composition sample obtained by roll-mixing components using a kneader was taken to measure the specific gravity prior to provision to an extruder, and expanded (foamed) through the extruder. The specific gravity of the expanding sample used as a support was measured, and compared with the specific gravity of the sample. To determine whether pre-foaming occurs or not in the mixing machine, the sample was compared with a flame-retardant composition without a microcapsule in Comparative Example 1, which has a specific gravity of 1.57, by examination with the naked eye.
2) Extrusion Test
The composition was roll-mixed using the kneader, and extruded so as to foam using an apparatus for forming a composite panel operated in a co-extrusion type, thereby completing a flame-retardant composite panel having a low specific gravity. Here, foam uniformity and bank uniformity on a calender roll were examined.
The thickness of an aluminum plate was 4 mm, the thickness of an alloy of each of the layers disposed on and under the plate was 0.5 mm, and the thickness of a support including an adhesive layer was 3 mm.
Criteria for foam uniformity and bank uniformity - ○:good, △: fair, X: bad
Here, specifications and temperatures for the extruder used are as follows.
(1) Specifications for Extruder
- Main Extruder
L/D = 12, Cylinder Diameter = 180 mm, Screw Compression Ratio = 1.2:1, T-die Width = 1250 mm
- Sub-Extruder
L/D = 30, Cylinder Diameter = 60 mm, Screw Compression Ratio = 1.9:1
(2) Extrusion Conditions
- Main Extruder (Heat-Expandable Flame-Retardant Polyolefin Resin)
Temperature: C1/C2/C3/Screen Changer/Adaptor/Feed Block = 170/180/190/195/195/195 ℃
- Sub-Extruder (Adhesive Resin)
Temperature: C1/C2/C3/C4/Adaptor = 130/150/170/190/190 ℃
- Temperature of T-die = 195 ℃
3) Flame-Retardant Property
A sample was manufactured using the aluminum composite panel formed above, and evaluated for flame-retardant property.
- Related Standard: Quasi-non-combustibility standard according to KS F5660-1
After the sample is irradiated with 50 kW/m2 of radiation, it should have a total amount of heat generated for 10 minutes of 8 MJ/m2 or less, and the maximum amount of heat emitted during the 10 minutes should not exceed 200 kW/m2 for 10 seconds or longer, and there should be no hole in the sample after the 10-minute heating.
- An oxygen index was evaluated according to ASTM D2863.
<Example 1>
Based on the total weight of the resin composition, a polyolefin resin composed of 15 parts by weight of linear low-density polyethylene (LLDPE, MI=20, Specific Gravity=0.924) [JL210, SK Energy, Co., Ltd., Korea] and 15 parts by weight of a metallocene polyolefin resin [Engage 8200, Dow Chemical Co., U.S.] and 69.5 parts by weight of inorganic magnesium hydroxide [DG-800, International Power Engineering Co., China] flame retardant were provided to a 110-liter kneader mixer [Fine Mechatronics, Co. Ltd., Korea] which was set to 120 ℃. When the mixture reached about 100 ℃, 0.5 parts by weight of a heat-expandable microcapsule [MSH-500, Matsumotousiseiyaku, Co., Ltd., Japan] was added thereto and melt-mixed to reach 125 ℃, thereby preparing a heat-expandable flame-retardant polyolefin resin composition (see Table 1).
Afterwards, the composition passed through a 180-mm single screw extruder with a T-die [Fine Mechatronics Co. Ltd., Korea] to expand (foam), and it was then provided to a calender roll, where aluminum panels were adhered on and under the extruded composition, thereby forming an aluminum composite panel at a rate of 2.4 meter per minute.
As a result, the composition had a specific gravity of 1.58 prior to foaming, and pre-foaming was not observed. Moreover, a support for the aluminum composite panel, which was obtained by foaming the composition, had a dramatic decrease in specific gravity to 1.16. The oxygen index was 54, and thus the flame-retardant property satisfied the quasi-non-combustibility standard according to KS F5660-1. During extrusion, good foam uniformity and bank formation were observed. The results are shown in Table 2.
<Example 2>
A process was performed in the same manner as in Example 1, except that 1 part by weight of the heat-expandable microcapsule was added while the ratio of the polyethylene resin to the inorganic flame retardant was the same as in Example 1 (see Table 1).
As a result, the specific gravity of the composition was 1.57 prior to the foaming, and pre-foaming was not observed. The specific gravity of the support was 0.96, which was similar to that of the polyethylene resin, and the oxygen index was 52.5, which means that the flame-retardant property satisfied the quasi-non-combustibility standard according to KS F5660-1. Good foam uniformity and bank formation were observed. The results are shown in Table 2.
<Example 3>
A process was performed in the same manner as in Example 1, except that 3 parts by weight of the heat-expandable microcapsule was added while the ratio of the polyethylene resin to the inorganic flame retardant was the same as in Example 1 (see Table 1).
As a result, the specific gravity of the composition was 1.55 prior to the foaming, and pre-foaming was not observed. The specific gravity of the support was 0.84, which was lower than that of the polyethylene resin. The oxygen index was 52, which means that the flame-retardant property satisfied the quasi-non-combustibility standard. However, the foam uniformity was slightly decreased, and the bank formation was also slightly non-uniform, which did not cause any major problems in the formation of the product. The results are shown in Table 2.
<Comparative Example 1>
A process was performed in the same manner as in Example 1, except that the heat-expandable microcapsule was not added (see Table 1).
As a result, the specific gravity of the support for the aluminum composite panel was 1.58, which was significantly higher than that of the polyethylene resin (e.g., 0.924). However, the oxygen index was 54, which means that the flame-retardant property satisfied the quasi-non-combustibility standard according to KS F5660-1. In addition, good bank formation was observed on the calender roll. The results are shown in Table 2.
<Comparative Example 2>
A process was performed in the same manner as in Example 1, except that 6 parts by weight of the heat-expandable microcapsule was added while the ratio of the polyethylene resin to the inorganic flame retardant was the same as in Example 1 (see Table 1).
As a result, the specific gravity of the composition was 1.53 prior to foaming, and pre-foaming was not observed. However, while the composition was extruded on the T-die, it was so non-uniform that it was almost impossible to form a bank. Accordingly, the formation of the aluminum composite panel failed. The results are shown in Table 2.
<Table 1>
Compositions of Heat-expandable Flame-Retardant Polyolefin Resin (Parts by weight)
Figure PCTKR2009006993-appb-I000001
In Table 1, LLDPE has a MI of 20, and a specific gravity of 0.924 [JL210, SK Energy Co., Korea], 1) metallocene polyolefin resin was Engage 8200, commercially available from Dow Chemical in the U.S., 2) magnesium hydroxide was DG-800, commercially available from International Powder Engineering Co. in China, and 3) heat-expandable microcapsule was MSH-500, commercially available from Matsumotousiseiyaku, Co., Ltd. in Japan.
<Table 2>
Properties of Compositions according to Examples and Comparative Examples
Figure PCTKR2009006993-appb-I000002
As shown in FIG. 2, it can be noted that when the composition was foamed by adding the heat-expandable microcapsule, compared with when no heat-expandable microcapsule was added, the specific gravity was significantly reduced, and there was almost no adverse effect on the flame-retardant property. Thus, it can be noted that, with almost the same flame-retardant property, the specific gravity can be similar to or lower than the polyethylene resin.
Consequently, a heat-expandable microcapsule is foamed to reduce the specific gravity, and an amount of a flame-retardant resin composition to be used per volume is reduced to make a panel lightweight and maintain a flame-retardant property, which leads to ease of handling and a reduction in production cost.
While exemplary embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes can be made to the described exemplary embodiments without departing from the spirit and scope of the invention defined by the claims and their equivalents.

Claims (18)

  1. A heat-expandable flame-retardant polyolefin resin composition, comprising:
    15 to 40 parts by weight of a polyolefin resin, 60 to 80 parts by weight of an inorganic flame retardant, and 0.2 to 5 parts by weight of a heat-expandable microcapsule.
  2. The composition according to claim 1, wherein the polyolefin resin is composed of 20 to 80 parts by weight of a polyethylene resin and 20 to 80 parts by weight of an ethylene copolymer, a thermoplastic rubber or a combination thereof, based on a total weight of the polyolefin resin.
  3. The composition according to claim 2, wherein the polyethylene resin includes at least one selected from low-density polyethylene, linear low-density polyethylene, and very low-density polyethylene.
  4. The composition according to claim 2, wherein the polyethylene resin has a density of 0.89 to 0.929 g/cm3, and a melt index of 10 to 60 g per 10 minutes.
  5. The composition according to claim 2, wherein the ethylene copolymer includes at least one selected from an ethylene-propylene copolymer, an ethylene-octene copolymer, an ethylene-butene copolymer, an ethylene-hexene copolymer, ethylene vinylacetate, ethylene ethylacrylate, and ethylene methylacrylate.
  6. The composition according to claim 2, wherein the thermoplastic rubber includes at least one selected from dynamic vulcanization products prepared by reaction of the polyolefin resins such as a styrene-butadiene-styrene (SBS) copolymer and a styrene-isoprene-styrene (SIS) copolymer with their hydrogenated products such as a styrene-ethylene-butylene-styrene (SEBS) copolymer and a styrene-ethylene-propylene-styrene (SEPS) copolymer, hydrogenated styrene-butadiene rubber (HSBR), and an ethylene-propylene-diene monomer (EPDM).
  7. The composition according to claim 1, wherein the inorganic flame retardant includes at least one selected from magnesium hydroxide, aluminum hydroxide, and magnesium carbonate.
  8. The composition according to claim 7, wherein the inorganic flame retardant has a particle size of 1 to 60 mm, and a specific surface area of 0.4 to 35 m2/g.
  9. The composition according to claim 1, wherein the heat-expandable microcapsule includes liquid hydrocarbon in a polymer shell having a size of 3 to 50 mm, and the polymer shell is formed of a nitrile copolymer.
  10. The composition according to claim 9, wherein the nitrile copolymer includes at least one selected from an acrylonitrile copolymer, a methacrylonitrile copolymer, an alpha-chloroacrylonitrile copolymer, an alpha-ethoxyacrylonitrile copolymer, and a fumaronitrile copolymer.
  11. The composition according to claim 9, wherein the heat-expandable microcapsule has an expansion initiation temperature which is equal to or higher than a melting point of the polyolefin resin, and a maximum expansion temperature of 150 to 220 ℃.
  12. A flame-retardant composite panel comprising a heat-expandable flame-retardant polyolefin resin composition according to any one of claims 1 through 11.
  13. A method of forming a flame-retardant composite panel, comprising:
    preparing a heat-expandable flame-retardant polyolefin resin composition by mixing 15 to 40 parts by weight of a polyolefin resin, 60 to 80 parts by weight of an inorganic flame retardant, and 0.2 to 5 parts by weight of a heat-expandable microcapsule, based on a total weight of the resin composition; and
    foaming the heat-expandable flame-retardant polyolefin resin composition and adhering the foamed heat-expandable flame-retardant polyolefin resin composition to a metal plate.
  14. The method according to claim 13, wherein preparing the heat-expandable flame-retardant polyolefin resin composition is performed in the range of 90 to 150 ℃.
  15. The method according to claim 13, wherein preparing the heat-expandable flame-retardant polyolefin resin composition includes mixing 15 to 40 parts by weight of the polyolefin resin with 60 to 80 parts by weight of the inorganic flame retardant based on the total weight of the resin composition at 90 to 120 ℃; and adding 0.2 to 5 parts by weight of the heat-expandable microcapsule to the mixture of the polyolefin resin and the inorganic flame retardant, to mix together at 120 to 150 ℃.
  16. The method according to claim 13, wherein foaming the heat-expandable flame-retardant polyolefin resin composition and adhering the foamed heat-expandable flame-retardant polyolefin resin composition to a metal plate is performed in the range of 150 to 220 ℃.
  17. The method according to claim 13, wherein the foaming is performed using a single screw extruder and a T-die.
  18. The method according to claim 17, wherein the single screw extruder has an L/D of 8 to 24, and a screw compression ratio of 1.1:1 to 2.5:1.
PCT/KR2009/006993 2008-11-25 2009-11-25 Heat-expandable flame-retardant polyolefin resin composition and flame-retardant composite panel using the same Ceased WO2010062113A2 (en)

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