CN1738859A - Flame retardant polypropylene resin composition with excellent weatherability - Google Patents

Flame retardant polypropylene resin composition with excellent weatherability Download PDF

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Publication number
CN1738859A
CN1738859A CNA2004800022503A CN200480002250A CN1738859A CN 1738859 A CN1738859 A CN 1738859A CN A2004800022503 A CNA2004800022503 A CN A2004800022503A CN 200480002250 A CN200480002250 A CN 200480002250A CN 1738859 A CN1738859 A CN 1738859A
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flame retardant
weight
gram
composition according
stabilizer
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CN100336858C (en
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郑仁植
曹再焕
许万生
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Hanwha TotalEnergies Petrochemical Co Ltd
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Samsung General Chemicals Co Ltd
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    • 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
    • C08L23/12—Polypropene
    • 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
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K5/02—Halogenated hydrocarbons
    • 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
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed herein is a flame retardant polypropylene resin composition with excellent weatherability. More specifically, the present invention relates to a flame retardant polypropylene composition comprising polypropylene resin having 4-40 g/10 min. melt flow index, halogen-based flame retardant having high-melting point, antimony oxide, inorganic filler, UV stabilizer, crosslinking agent and dripping-resistant agent. Using the composition of the present invention, there may be provided secondary product which has fire retardancy, maintainability of excellent early fire retardancy under the long term-UV exposure and hot water process, high-weatherability, and excellent mechanical property.

Description

Flame retardant polypropylene resin composition with good weather resisteant
Technical field
The present invention relates to contain the flame retardant polypropylene resin composition of acrylic resin as main ingredient.More specifically, the present invention relates to have the flame retardant polypropylene resin composition of good weather resisteant, it is 4-40 gram/10 minutes acrylic resin, high-melting-point halogen-based flame retardant, flame-retardant additive, UV stabilizer, linking agent and Antidrip agent that said composition contains melt flow index.Even this flame retardant polypropylene resin composition was soaked the flame retardant resistance in the time of also keeping beginning and was shown the high-mechanical property retention in hot water.
Background technology
Because acrylic resin has good processibility, chemical resistant properties, physical strength etc., therefore be widely used in every field, for example household electrical appliance, material of construction, house decorative material and various trolley part.Yet, because the poor fire of acrylic resin, thereby be restricted in the application aspect trolley part with very big fire and the electric/electronic.For this reason, in a large number inorganic about adding, organically and phosphine flame retardant just actively develop with the research of giving various polyolefin resin excellent flame retardancy.
For example, open 53-92855,54-29350 of Japan special permission, 54-77658,56-26954,57-87462,60-110738 disclose by adding magnesium hydroxide as inorganic combustion inhibitor, aluminium hydroxide, hydrotalcite etc. to give the method that the acrylic resin flame retardant resistance prepares flame retardant polypropylene resin composition.Yet some problem of aforesaid method because in order to obtain the combustibility of V-0 level, must add 50% or more high-load mineral filler, thus cause the processing characteristics of acrylic resin very poor, product may emit gas and shock strength sharply descends.
Japan special permission communique 55-30739 has reported the retardant polypropylene resin that makes as the halogen compounds of organic fire-retardant such as decabromodiphynly oxide and 12 chloro-, ten dihydro methylene radical hexichol cyclooctene by adding.The method for preparing flame retardant polypropylene resin composition by interpolation tetrabromo-bisphenol two (dibromopropyl ether), two (tribromo-benzene oxygen ethyl) tetra bromobisphenol A ethers, hexabromocyclododecane and tetrabromo-bisphenol also has been public institute cicada.
The open Hei 8-302102 of Japan's special permission discloses the flame retardant polypropylene resin composition with improved anti-bloom and weather resisteant, and said composition contains organic halogenizing compound and contains the halogenation epoxy oligomeric flame retardants of bromine.Although above-mentioned composition has outstanding initial flame retardant resistance and processibility, weather resisteant and solar heat protection water-based energy still are very poor.Therefore, after hot-water soak or exposing to the open air for a long time under UV-light, its initial flame retardant resistance sharply descends, and mechanical property is difficult to keep.For above-mentioned reasons, conventional composition can not be used for the light bulb holder of outdoor products such as artificial Christmas, because they contact with rainwater with external environment such as light usually for a long time.
Summary of the invention
Therefore, finished the present invention in view of the above problems.Feature of the present invention provides the flame retardant polypropylene resin composition that can be processed into secondary product, even this secondary product has good initial flame retardant resistance and exposes its weather resisteant and also highly reservation of mechanicalness under light for a long time to the open air, and heat-resisting water logging bubble.Also can show good flame retardant resistance even thickness is very little.
Consistent with feature of the present invention, the invention provides a kind of flame retardant polypropylene resin composition, its melt flow index that contains (A) 37-67 weight % is/10 minutes a acrylic resin of 4-40 gram; (B) the high-melting-point halogen-based flame retardant of 17-29 weight %; (C) weisspiessglanz of the white powder of 4-14 weight %; (D) mineral filler of 2-22 weight %; (E) UV stabilizer of 0.35-4.0% weight; (F) particulate tetrafluoroethylene polymer of 0.15-2.5 weight %; (G) linking agent of 0.08-3.5 weight %.
Describe the present invention below in detail.
Crystalline polypropylene homopolymer or crystalline polypropylene multipolymer and be selected from least a compound in the group of forming by ethene, 1-butylene, 1-amylene, 1-hexene, 4-methylpentene, 1-heptene, 1-octene and 1-decene and can be used as acrylic resin (A) in the flame retardant polypropylene resin composition of the present invention.Preferred crystalline polypropylene homopolymer.The melt flow index of acrylic resin (A) is preferably 4-40 gram/10 minutes, and more preferably the 5-30 gram is/10 minutes.In the resin combination gross weight, the content of acrylic resin (A) in 37-67 weight % scope, preferred 45-65 weight %.
The example of high-melting-point halogen-based flame retardant (B) comprises decabromodiphynly oxide, ethene-two (tetrabromo phthalimide), two pentabromobenzene oxidative ethane and their mixture.Particularly, decabromodiphynly oxide (S-102E, Albemarle company), ethene-two (tetrabromo phthalimide) (BT-93, Albemarle company) or all commercially available the getting of two pentabromobenzene oxidative ethane (S-8010, Albemarle company).In the resin combination gross weight, the amount of the preferred high-melting-point halogen-based flame retardant of the present invention (B) is 17-29 weight %.When the add-on of fire retardant was lower than 17 weight %, the combustibility when thickness is 1/32 inch did not reach the V-0 level.On the other hand, when the add-on of fire retardant surpassed 29 weight %, weather resisteant was very poor, and mechanical property keeps low too.
Weisspiessglanz is as contained flame retardant additives (C) in the resin combination of the present invention.The specific examples of weisspiessglanz comprises ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide and their mixture.The amount of the weisspiessglanz that adds preferably in 4-14 weight % scope, more preferably 5-12 weight %.
Contained mineral filler (D) is talcum, barium sulfate, lime carbonate or their mixture in the resin combination of the present invention.The add-on of mineral filler (D) is preferably 2-22 weight %, more preferably 4-15 weight %.
The composition of preferred uv-absorbing agent and HALS based stabilizer is as contained UV stabilizer (E) in the resin combination of the present invention.HALS based stabilizer preferred molecular weight is 2000 or higher.When the molecular weight of HALS based stabilizer was lower than 2000, UV stabilizer was tending towards bloom from gained secondary processing composition, and thereby can not obtain long-term ultraviolet stability.The preferred add-on of uv-absorbing agent and HALS base UV stabilizer is 0.12-2.0 weight %, and the total amount of UV stabilizer (E) is 0.35-4.0 weight % like this.If add UV stabilizer or HALS based stabilizer separately, also can obtain V-0 level combustibility, but that the tensile yield strength after the term UV exposure keeps is very low, and thereby can not obtains to belong to the anti-set of circumstances compound that the high physicals of having of f1 level keeps.
Being included in particulate tetrafluoroethylene polymer (F) in the resin combination of the present invention, preferably to have fluorine content be 65-76 weight %, more preferably 70-76 weight %.In addition, but also can use the multipolymer of tetrafluoro ethylene polymer, fluorochemical monomer and tetrafluoroethylene or copolymerization and the not fluorine-containing ethylenically unsaturated monomers and the multipolymer of tetrafluoroethylene.When molded resin composition, tetrafluoroethylene exists with the fibril form, and burning can stop metallic substance drippage (dripping) during moulded parts.The granular tetrafluoroethylene of preferred use, can obtain by method of the prior art (referring to Houden-Weyl, Metrodender OrganischemChemie, Volume 14/1, p 842-849, Stuttgart, 1961).The add-on of particulate tetrafluoroethylene polymer is preferably in 0.15-2.5 weight % scope.When the content of particulate tetrafluoroethylene polymer is lower than 0.15 weight %, can not fully obtain the flammable required anti-drippage effect of V-0 level.At this moment, because combustion thickness is the drippage of 1/32 inch molten resin, V-0 level combustibility can not get guaranteeing.When the content of particulate tetrafluoroethylene polymer was lower than 2.5 weight %, excessive particulate tetrafluoroethylene polymer was to the not contribution of the anti-drippage of further raising effect, and greatly worsened resin flow, made the molding processing difficulties.
The example that can be used as linking agent contained in the resin combination of the present invention (G) comprises polyfunctional monomer, oxime-nitroso compound, maleimide compound etc.Particularly, can use cyanacrylate, (two) ethylene glycol bisthioglycolate (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane (methyl) acrylate, Viscoat 295, Viscoat 295, pentaerythritol triacrylate, tetramethylol methane tetraacrylate etc.Preferably multifunctional (methyl) acrylate such as trimethylolpropane tris (methyl) acrylate and tetramethylolmethane (methyl) acrylate.The add-on of linking agent in 0.08-3.5 weight % scope, preferred 0.2-2 weight %.When the amount of linking agent is lower than 0.1 weight %, expose the poor stability under ultraviolet to the open air, and thereby term UV exposure after physicals keep variation.When the amount of linking agent is higher than 3 weight %, can form apparent imperfection such as ripple during molding, make that final molded article surface is rough.
It is 1/32 inch, flammable excellent flame retardancy during for the V-0 level that flame retardant polypropylene resin composition of the present invention shows corresponding to thickness, as measuring with the vertical flammability test of describing among the UL Subject 94 in " flammability test that is used for the plastic material of mechanical part " (hereinafter to be referred as " UL 94 vertical flammability tests "), simultaneously, even also keep identical flammable rank through after long illumination and the hot-water soak.And, even flame retardant polypropylene resin composition of the present invention also keeps initial flame retardant resistance after long-time illumination and long-time hot-water soak, as with describe among the UL Subject 746C the measuring of " being used for the anti-environment test of the plastic material of mechanical part " based on weather resisteant and soaking-resistant test (hereinafter to be referred as " UL 746 anti-environment tests "), and show high mechanical property simultaneously and keep.Therefore, resin combination of the present invention can be used as suitable material, material of construction, indoor/outdoor finishing material and the trolley part that indoor/outdoor is used that be used for.
Embodiment
Followingly describe the present invention with reference to embodiment.Yet these embodiment only are used to illustrate the present invention rather than to any restriction of the scope of the invention.
Embodiment 1
5.9 being/10 minutes crystalline polypropylene homopolymer of 8 grams, kilogram melt flow index (is 2.16 kilograms 230 ℃ following 10 minutes melt flow in load) restrains ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb as high-melting-point halogen-based flame retardant, 700 as acrylic resin, 2.4 kilograms of two pentabromobenzene oxidative ethanes (S-8010, Albemarle company) 2O 3Ilsung Antimony company limited) as flame-retardant additive, 1.0 (KCM 6300 for the kilogram talcum, KOCH) as mineral filler, (Tinuvin 326 for 50 gram uv-absorbing agents, CIBA GEIGY), 50 gram HALS base UV stabilizer (Chimabsorber 944FD, CIBA GEIGY), 50 gram particle shape tetrafluoro ethylene polymer (Teflon 800J, Dupont) as anti-dripping agent, 50 gram linking agent (A-TMM-3L, Nippon Chemical, Japan), 10 gram calcium stearates, (IRGANOX 1010 for 20 gram antioxidants, CIBA GEIGY) and 20 the gram antioxidants (IRGAFOS 168, CIBA GEIGY) puts in the Henschel mixing tank as other additives, mixture was stirred 3 minutes, afterwards the gained mixture is sent into (diameter: 30 millimeters) in the twin screw extruder machine, melted and extrude and make bead at 190 ℃.With above-mentioned bead drying under 100 ℃ was that 300 ℃ of injection molding machines carry out molding with the preparation testing plate with maximum center housing temperature also in 3 hours.Measure the flame retardant resistance and the tensile yield strength of above-mentioned testing plate.The result is as shown in table 1 below.
Handle
In UL Subject 746C (Underwrites Laboratories Incorporation), describe under the weather resisteant test condition of " being used for the anti-environment test of the plastic material of mechanical part ", testing plate exposes that (uv irradiating dosage is 0.35 watt/square metre (340nm) in the Xenon Arc UV-light the same with ASTM 2565Type A standard method to the open air, blackboard temperature: 63 ℃, the Water ejection-type) under.Testing plate placed in 70 ℃ of water-baths carried out hot-water soak in 7 days and handle.Afterwards, measure the flame retardant resistance and the mechanical property of testing plate.
Evaluation method
The flame retardant resistance of testing plate is by estimating with the vertical flammability test of describing among the UL Subject 94 (Underwriters Laboratories company) (V0) in " flammability test that is used for the plastic material of mechanical part ".Thickness in this used testing plate is 1/32 inch.The tensile impact strength of testing plate uses the tensile impact device (TOYOSEIKI, Japan) the same with ASTM D-1822 standard method to estimate with keeping.Thickness in this used testing plate (S type) is 1/32 inch.
Level evaluation
-f1 represents the flammable V-0 level that is, the tensile impact strength in the term UV exposure test be left 70% or higher and in the hot-water soak test, be 50% or higher;
-f2 represents the flammable V-0 level that is, the tensile impact strength in the term UV exposure test be left 70% or higher, or in the hot-water soak test, be 50% or higher; With
-when the reservation of flammable and tensile impact strength was not less than f1 or f2, rank was represented with " * ".
Embodiment 2-4 and Comparative Examples 1 and 2
Repeat the step of embodiment 1, except the add-on as two pentabromobenzene oxidative ethanes (S-8010, Albemarle company) of fire retardant as shown in table 1 below.The result is as shown in table 1.
The result of the embodiment 1-4 shown in the comparison sheet 1 and Comparative Examples 1 and 2, at two pentabromobenzene oxidative ethane (S-8010 as fire retardant, Albemarle company) join under the anti-dripping agent and the situation in the linking agent of specified quantitative with appropriate vol, flammable V-0 level remain unchanged and the reservation of tensile impact strength very high.In addition, even when hot-water soak, flammable V-0 level still remain unchanged and the reservation of tensile impact strength very high.Therefore, resin combination shows the excellent environment resistance that belongs to specified f1 level among the UL 746C.
Embodiment 5
6.1 being/10 minutes crystalline polypropylene homopolymer of 8 grams, kilogram melt flow index (is 2.16 kilograms 230 ℃ following 10 minutes melt flow in load) restrains ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb as high-melting-point halogen-based flame retardant, 500 as acrylic resin, 2.4 kilograms of two pentabromobenzene oxidative ethanes (S-8010, Albemarle company) 2O 3Ilsung Antimony company limited) as flame-retardant additive, 1.0 (KCM 6300 for the kilogram talcum, KOCH) as mineral filler, (Tinuvin 326 for 50 gram uv-absorbing agents, CIBA GEIGY), 50 gram HALS base UV stabilizer (Chimabsorber 944FD, CIBA GEIGY), 50 gram particle shape tetrafluoro ethylene polymer (Teflon 800J, Dupont) as anti-dripping agent, 50 gram linking agent (A-TMM-3L, Nippon Chemical, Japan), 10 gram calcium stearates, (IRGANOX 1010 for 20 gram antioxidants, CIBA GEIGY) and 20 the gram antioxidants (IRGAFOS 168, CIBA GEIGY) puts in the Henschel mixing tank as other additives, mixture was stirred 3 minutes, afterwards the gained mixture is sent into (diameter: 30 millimeters) in the twin screw extruder machine, melted and extrude and make bead at 190 ℃.With above-mentioned bead drying under 100 ℃ was that 200 ℃ of injection molding machines carry out molding with the preparation testing plate with maximum center housing temperature also in 3 hours.Measure the flame retardant resistance and the tensile yield strength of above-mentioned testing plate.The result is as shown in table 1 below.
Embodiment 6 and Comparative Examples 3 and 4
Repeat the step of embodiment 5, except the add-on as three ANTIMONY TRIOXIDE SB 203 99.8 PCT of flame retardant additives as shown in table 1.The result is as shown in table 1.
Embodiment 5 and 6 and the result of Comparative Examples 3 and 4 has only when the add-on of flame retardant additives surpasses predetermined amount, even flame retardant resistance also keeps good in term UV exposure and hot-water soak in the comparison sheet 1.When the add-on as three ANTIMONY TRIOXIDE SB 203 99.8 PCT of flame retardant additives surpasses 14 weight %, flame retardant resistance no longer rises.On the other hand, when the add-on as three ANTIMONY TRIOXIDE SB 203 99.8 PCT of flame retardant additives was lower than 4 weight %, physicals kept very low, and thereby can not obtain to belong to the anti-environment of f1 level.
Embodiment 7
6.4 being/10 minutes crystalline polypropylene homopolymer of 8 grams, kilogram melt flow index (is 2.16 kilograms 230 ℃ following 10 minutes melt flow in load) restrains ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb as high-melting-point halogen-based flame retardant, 700 as acrylic resin, 2.4 kilograms of two pentabromobenzene oxidative ethanes (S-8010, Albemarle company) 2O 3Ilsung Antimony company limited) as flame-retardant additive, (KCM 6300 for 500 gram talcums, KOCH) as mineral filler, (Tinuvin 326 for 50 gram uv-absorbing agents, CIBA GEIGY), 50 gram HALS base UV stabilizer (Chimabsorber 944FD, CIBA GEIGY), 50 gram particle shape tetrafluoro ethylene polymer (Teflon 800J, Dupont) as anti-dripping agent, 50 gram linking agent (A-TMM-3L, NipponChemical, Japan), 10 gram calcium stearates, (IRGANOX 1010 for 10 gram antioxidants, CIBAGEIGY) and 20 the gram antioxidants (IRGAFOS 168, CIBA GEIGY) puts in the Henschel mixing tank as other additives, mixture was stirred 3 minutes, afterwards the gained mixture is sent into (diameter: 30 millimeters) in the twin screw extruder machine, melted and extrude and make bead at 190 ℃.With above-mentioned bead drying under 100 ℃ was that 200 ℃ of injection molding machines carry out molding with the preparation testing plate with maximum center housing temperature also in 3 hours.Measure the flame retardant resistance and the tensile yield strength of above-mentioned testing plate.The result is as shown in table 1 below.
Embodiment 8 and 9 and Comparative Examples 5 and 6
Repeat the step of embodiment 7, (KCM 6300, and KOCH) add-on with acrylic resin changes over as shown in table 1 except the talcum as mineral filler.The result is as shown in table 1.
From table 1, can obviously find out, influence flame retardant resistance greatly as the talcum of mineral filler.When the steatitic amount is less than 2 weight %, can obtain the flammable flame retardant resistance of the specified V-0 of belonging to level in UL Subject 94.And talc content is during greater than 22 weight %, and tensile impact strength keeps very low.Therefore, in order to obtain the flame retardant resistance that better physicals keeps and belong to the f1 level, the content of mineral filler should be in 3-20 weight % scope.
Embodiment 10
5.9 being/10 minutes crystalline polypropylene homopolymer of 8 grams, kilogram melt flow index (is 2.16 kilograms 230 ℃ following 10 minutes melt flow in load) restrains ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb as high-melting-point halogen-based flame retardant, 700 as acrylic resin, 2.4 kilograms of two pentabromobenzene oxidative ethanes (S-8010, Albemarle company) 2O 3Ilsung Antimony company limited) as flame-retardant additive, 1.0 (KCM 6300 for the kilogram talcum, KOCH) as mineral filler, (Tinuvin 326 for 200 gram uv-absorbing agents, CIBA GEIGY), 50 gram HALS base UV stabilizer (Chimabsorber 944FD, CIBA GEIGY), 50 gram particle shape tetrafluoro ethylene polymer (Teflon 800J, Dupont) as anti-dripping agent, 50 gram linking agent (A-TMM-3L, Nippon Chemical, Japan), 10 gram calcium stearates, (IRGANOX 1010 for 20 gram antioxidants, CIBA GEIGY) and 20 the gram antioxidants (IRGAFOS 168, CIBA GEIGY) puts in the Henschel mixing tank as other additives, mixture was stirred 3 minutes, afterwards the gained mixture is sent into (diameter: 30 millimeters) in the twin screw extruder machine, melted and extrude and make bead at 190 ℃.With above-mentioned bead drying under 100 ℃ was that 200 ℃ of injection molding machines carry out molding with the preparation testing plate with maximum center housing temperature also in 3 hours.Measure the flame retardant resistance and the tensile yield strength of above-mentioned testing plate.The result is as shown in table 2 below.
Embodiment 11 and Comparative Examples 7 and 8
Repeat the step of embodiment 10, except the amount of uv-absorbing agent (Tinuvin 326, CIBA GEIGY) changes over shown in the table 2.
The injection molding machine that is set in 200 ℃ with maximum center housing temperature carries out molding with the preparation testing plate with the bead of gained in embodiment 11 and Comparative Examples 7 and 8.Measure the flame retardant resistance and the tensile impact strength of testing plate.The result is as shown in table 2 below.
Data can obviously be found out from table 2, show very high reservation even add behind the uv-absorbing agent tensile impact strength that exposes to the open air in the mechanical property down in UV-light, and thereby show the improved anti-environment that belongs to specified f1 level among the UL 736C.When the add-on of uv-absorbing agent was lower than 0.15 weight %, ultraviolet absorbability was very poor.Simultaneously, when the add-on of uv-absorbing agent surpassed 2 weight %, ultraviolet absorbability was good but because the surperficial frosting of layered product causes the outward appearance of moulded parts very poor.Therefore, find that the add-on of uv-absorbing agent is preferably in the 0.15-2 weight range.
Embodiment 12
5.9 being/10 minutes crystalline polypropylene homopolymer of 8 grams, kilogram melt flow index (is 2.16 kilograms 230 ℃ following 10 minutes melt flow in load) restrains ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb as high-melting-point halogen-based flame retardant, 700 as acrylic resin, 2.4 kilograms of two pentabromobenzene oxidative ethanes (S-8010, Albemarle company) 2O 3Ilsung Antimony company limited) as flame-retardant additive, 1.0 (KCM 6300 for the kilogram talcum, KOCH) as mineral filler, (Tinuvin 326 for 50 gram uv-absorbing agents, CIBA GEIGY), 200 gram HALS base UV stabilizer (Chimabsorber 944FD, CIBA GEIGY), 50 gram particle shape tetrafluoro ethylene polymer (Teflon 800J, Dupont) as anti-dripping agent, 50 gram linking agent (A-TMM-3L, Nippon Chemical, Japan), 10 gram calcium stearates, (IRGANOX 1010 for 20 gram antioxidants, CIBA GEIGY) and 20 the gram antioxidants (IRGAFOS 168, CIBA GEIGY) puts in the Henschel mixing tank as other additives, mixture was stirred 3 minutes, afterwards the gained mixture is sent into (diameter: 30 millimeters) in the twin screw extruder machine, melted and extrude and make bead at 190 ℃.With above-mentioned bead drying under 100 ℃ was that 200 ℃ of injection molding machines carry out molding with the preparation testing plate with maximum center housing temperature also in 3 hours.Measure the flame retardant resistance and the tensile yield strength of above-mentioned testing plate.The result is as shown in table 2 below.
Embodiment 13 and Comparative Examples 9-13
Repeat the step of embodiment 12,, and do not add PETA as linking agent except the content of HALS base UV stabilizer becomes shown in the table 2 with type change.The result is as shown in table 2.
From table 2, can obviously find out, when not adding linking agent, can obtain required flame retardant resistance (1/32 inch) when using various HALS base UV stabilizer.Yet,, therefore can not obtain to belong to the anti-environment of f1 level owing to very low in the mechanical tensile impact strength reservation that exposes to the open air for a long time under the xenon arc ultraviolet.
Embodiment 14
5.9 being/10 minutes crystalline polypropylene homopolymer of 8 grams, kilogram melt flow index (is 2.16 kilograms 230 ℃ following 10 minutes melt flow in load) restrains ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb as high-melting-point halogen-based flame retardant, 700 as acrylic resin, 2.4 kilograms of two pentabromobenzene oxidative ethanes (S-8010, Albemarle company) 2O 3Ilsung Antimony company limited) as flame-retardant additive, 1.0 (KCM 6300 for the kilogram talcum, KOCH) as mineral filler, (Tinuvin 326 for 50 gram uv-absorbing agents, CIBA GEIGY), 50 gram HALS base UV stabilizer (Chimabsorber 944FD, CIBA GEIGY), 50 gram particle shape tetrafluoro ethylene polymer (Teflon 800J, Dupont) as anti-dripping agent, 10 gram linking agent (A-TMM-3L, Nippon Chemical, Japan), 10 gram calcium stearates, (IRGANOX 1010 for 20 gram antioxidants, CIBA GEIGY) and 20 the gram antioxidants (IRGAFOS 168, CIBA GEIGY) puts in the Henschel mixing tank as other additives, mixture was stirred 3 minutes, afterwards the gained mixture is sent into (diameter: 30 millimeters) in the twin screw extruder machine, melted and extrude and make bead at 190 ℃.With above-mentioned bead drying under 100 ℃ was that 200 ℃ of injection molding machines carry out molding with the preparation testing plate with maximum center housing temperature also in 3 hours.Measure the flame retardant resistance and the tensile yield strength of above-mentioned testing plate.The result is as shown in table 2 below.
Embodiment 15 and 16 and Comparative Examples 14-16
Repeat the step of embodiment 14, except the content of linking agent change over shown in the table 2 like that.The result is as shown in table 2.
Embodiment 17 and 18
Repeat the step of embodiment 14, except the type change of linking agent become shown in the table 3a like that, the result is shown in table 3b.
As can be seen from Table 2, when the add-on of linking agent is suitable, can makes and have the moulded parts that high-mechanical property keeps.When the add-on of linking agent was less than 0.08 weight %, the mechanical property under the long-time term UV exposure kept quite low, and thereby can not obtain to belong to the anti-environment of f1 level.Yet when the add-on of linking agent surpassed 3.5 weight %, flame retardant resistance was very poor and thereby can not obtain the flammable flame retardant resistance of the specified V-0 of belonging to level in ULSubject 94.
From table 3b as can be seen, all tetramethylolmethane based cross-linkers all remain with contribution and can improve flame retardant resistance and anti-environment high-mechanical property.
Embodiment 20
5.9 being/10 minutes crystalline polypropylene homopolymer of 8 grams, kilogram melt flow index (is 2.16 kilograms 230 ℃ following 10 minutes melt flow in load) restrains ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb as high-melting-point halogen-based flame retardant, 700 as acrylic resin, 2.4 kilograms of two pentabromobenzene oxidative ethanes (S-8010, Albemarle company) 2O 3Ilsung Antimony company limited) as flame-retardant additive, 1.0 (KCM 6300 for the kilogram talcum, KOCH) as mineral filler, (Tinuvin 326 for 50 gram uv-absorbing agents, CIBA GEIGY), 50 gram HALS base UV stabilizer (Chimabsorber 944FD, CIBA GEIGY), 50 gram particle shape tetrafluoro ethylene polymer (7AJ, Dupont) as anti-dripping agent, 50 gram linking agent (A-TMM-3L, NipponChemical, Japan), 10 gram calcium stearates, (IRGANOX 1010 for 10 antioxidants, CIBAGEIGY) and 20 the gram antioxidants (IRGAFOS 168, CIBA GEIGY) puts in the Henschel mixing tank as other additives, mixture was stirred 3 minutes, afterwards the gained mixture is sent into (diameter: 30 millimeters) in the twin screw extruder machine, melted and extrude and make bead at 190 ℃.With above-mentioned bead drying under 100 ℃ was that 200 ℃ of injection molding machines carry out molding with the preparation testing plate with maximum center housing temperature also in 3 hours.Measure the flame retardant resistance and the tensile yield strength of above-mentioned testing plate.The result is shown in following table 3b.
Embodiment 21 and comparative example 17-19
Repeat the step of embodiment 14, except the content of particulate tetrafluoroethylene polymer change over shown in the table 3a like that.The result is shown in table 3b.
3b can obviously find out from table, when the add-on of particulate tetrafluoroethylene polymer is less than 0.15 weight %, does not observe anti-drippage effect, and thereby has drip phenomenon to take place when burning.Therefore, can not obtain the flammable flame retardant resistance of the specified V-0 of belonging to level in UL Subject 94.On the other hand, when the add-on of particulate tetrafluoroethylene polymer surpasses 2.5 weight %, impatient acute decline of resin flow, and estimate that anti-drippage effect does not improve yet.Therefore, though the appropriate amount of particulate tetrafluoroethylene polymer can guarantee flame retardant resistance and keep in the tensile impact strength that belongs to the f1 level that exposes to the open air for a long time under ultraviolet.
Embodiment 22
5.9 being/10 minutes crystalline polypropylene homopolymer of 8 grams, kilogram melt flow index (is 2.16 kilograms 230 ℃ following 10 minutes melt flow in load) restrains ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb as high-melting-point halogen-based flame retardant, 700 as acrylic resin, 2.4 kg ethylene-two (tetrabromo phthalimide) (BT-93, Albemarle company) 2O 3Ilsung Antimony company limited) as flame-retardant additive, 1.0 (KCM 6300 for the kilogram talcum, KOCH) as mineral filler, (Tinuvin 326 for 50 gram uv-absorbing agents, CIBAGEIGY), 50 gram HALS base UV stabilizer (Chimabsorber 944FD, CIBA GEIGY), 50 gram particle shape tetrafluoro ethylene polymer (Teflon 800J, Dupont), 50 gram linking agent (3-MM-T, Nippon Chemical, Japan), 20 gram calcium stearates, (IRGANOX 1010 for 20 antioxidants, CIBAGEIGY) and 20 the gram antioxidants (IRGAFOS 168, CIBA GEIGY) puts in the Henschel mixing tank as other additives, mixture was stirred 3 minutes, afterwards the gained mixture is sent into (diameter: 30 millimeters) in the twin screw extruder machine, melted and extrude and make bead at 190 ℃.With above-mentioned bead drying under 100 ℃ was that 200 ℃ of injection molding machines carry out molding with the preparation testing plate with maximum center housing temperature also in 3 hours.Measure the flame retardant resistance and the tensile yield strength of above-mentioned testing plate.The result is shown in following table 3b.
Embodiment 23 and Comparative Examples 20 and 21
Repeat the step of embodiment 22, except the kind of high-melting-point fire retardant change over shown in the table 3a like that, perhaps replace the high-melting-point fire retardant with the low melting point fire retardant.The result is shown in table 3b.
From the table 3b as can be seen, the composition that contains high-melting-point halogen-based flame retardant, particulate tetrafluoroethylene polymer and linking agent all shows good initial flame retardant resistance before and after term UV exposure and hot-water soak and high physicals keeps, to flame retardant resistance without any destruction.On the contrary, it is very poor to contain the flame retardant resistance that the flame retardant resin composition of low melting point halogen-based flame retardant shows after term UV exposure and hot-water soak.Particularly, the flame retardant composition that contains the low melting point halogen-based flame retardant before and after term UV exposure and hot-water soak, show 70% or lower physicals keep, and can not keep flame retardant resistance after the hot-water soak.Therefore, said composition can not satisfy the requirement of QMTO2 class definition, this QMTO2 categorised regulation be used for artificial Christmas the required high physicals of the polymer materials of light bulb holder keep and flame retardant resistance.
Table 1
The embodiment numbering Component Before the processing After the term UV exposure (1000 hours) After the hot-water soak (168 hours, 24 days) The final evaluation
A B-1 C D E-1 E-2 F G-1 1/32 inch of flame retardant resistance Tensile impact strength 1/32 inch of flame retardant resistance Tensile impact strength Tensile impact strength keeps 1/32 inch of flame retardant resistance Tensile impact strength Tensile impact strength keeps
Real 1 59 24 7 10 0.5 0.5 0.5 0.5 V-0 15.3 V-0 11.8 77％ V-0 13.5 88％ f1
Real 2 61 22 7 10 0.5 0.5 0.5 0.5 V-0 16.3 V-0 13.8 85％ V-0 14.2 87％ f1
Real 3 60 18 7 15 0.5 0.5 0.5 0.5 V-0 18.1 V-0 15.9 88％ V-0 15.3 85％ f1
Real 4 60 28 7 5 0.5 0.5 0.5 0.5 V-0 12.5 V-0 10.2 82％ V-0 11.9 95％ f1
To 1 53 30 7 10 0.5 0.5 0.5 0.5 V-0 11.8 V-0 7.1 60％ V-0 8.0 68％ ×
To 2 63 15 7 15 0.5 0.5 0.5 0.5 V-2 18.9 V-2 15.4 81％ V-2 13.8 73％ ×
Real 5 61 24 5 10 0.5 0.5 0.5 0.5 V-0 15.8 V-0 14.9 94％ V-0 12.6 80％ f1
Real 6 56 24 10 10 0.5 0.5 0.5 0.5 V-0 14.2 V-0 13.1 92％ V-0 13.5 95％ f1
To 3 63 24 3 10 0.5 0.5 0.5 0.5 V-2 16.9 V-2 14.3 85％ V-2 12.8 76％ ×
To 4 51 24 15 10 0.5 0.5 0.5 0.5 V-0 13.5 V-0 9.0 67％ V-0 11.5 85％ f2
Real 7 64 24 7 5 0.5 0.5 0.5 0.5 V-0 19.2 V-0 18.4 96％ V-0 15.3 80％ f1
Real 8 62 28 7 3 0.5 0.5 0.5 0.5 V-0 19.9 V-0 17.4 87％ V-0 16.1 81％ f1
Real 9 51 22 7 20 0.5 0.5 0.5 0.5 V-0 11.5 V-0 8.4 73％ V-0 10.6 92％ f1
To 5 65 28 7 - 0.5 0.5 0.5 0.5 V-2 20.4 V-2 17.4 85％ V-2 16.5 81％ ×
To 6 39 24 7 30 0.5 0.5 0.5 0.5 V-0 10.7 V-0 5.4 50％ V-0 8.1 76％ f2
Table 2
The embodiment numbering Component Before the processing After the term UV exposure (1000 hours) After the hot-water soak (168 hours, 24 days) The final evaluation
A B-1 C D E-1 E-2 * F G-1 1/32 inch of flame retardant resistance Tensile impact strength 1/32 inch of flame retardant resistance Tensile impact strength Tensile impact strength keeps 1/32 inch of flame retardant resistance Tensile impact strength Tensile impact strength keeps
Real 10 59 24 7 10 2.0 0.5 0.5 0.5 V-0 15.8 V-0 12.8 81％ V-0 13.8 87％ f1
Real 11 59 24 7 10 0.2 0.5 0.5 0.5 V-0 15.4 V-0 14.8 96％ V-0 13.9 90％ f1
To 7 59 24 7 10 0.1 0.5 0.5 0.5 V-0 15.2 V-0 10.1 66％ V-0 11.2 74％ f2
To 8 59 24 7 10 3.0 0.5 0.5 0.5 V-0 16.4 V-0 10.4 63％ V-0 13.4 82％ F2
Real 12 59 24 7 10 0.5 2.0 0.5 0.5 V-0 14.8 V-0 13.4 91％ V-0 13.2 89％ f1
Real 13 59 24 7 10 0.5 0.15 0.5 0.5 V-2 16.8 V-2 12.3 73％ V-2 13.5 80％ f1
To 9 59 24 7 10 0.5 0.1 0.5 0.5 V-0 15.7 V-0 10.1 64％ V-0 8.9 57％ ×
To 10 59 24 7 10 0.5 3.0 0.5 0.5 V-0 16.4 V-0 9.5 58％ V-0 10.8 66％ ×
To 11 59 24 7 10 0.5 - 0.5 - V-0 18.4 V-0 9.6 52％ V-0 11.5 63％ ×
To 12 59 24 7 10 0.5 - 0.5 - V-0 16.4 V-0 10.5 64％ V-0 10.5 64％ ×
Real 13 59 24 7 10 0.5 - 0.5 - V-0 15.9 V-0 9.4 59％ V-0 9.7 61％ ×
Real 14 59 24 7 10 0.5 0.5 0.5 0.1 V-0 18.4 V-0 13.6 74％ V-0 13.8 75％ f1
Real 15 59 24 7 10 0.5 0.5 0.5 0.2 V-0 15.2 V-0 13.9 91％ V-0 14.8 97％ f1
Real 16 59 24 7 10 0.5 0.5 0.5 3.0 V-0 16.3 V-0 15.0 92％ V-0 16.1 99％ f1
To 14 59 24 7 10 0.5 0.5 0.5 - V-0 14.3 V-0 8.4 59％ V-0 8.7 61％ ×
To 15 59 24 7 10 0.5 0.5 0.5 0.05 V-0 17.1 V-0 10.8 63％ V-0 8.9 52％ ×
To 16 59 24 7 10 0.5 0.5 0.5 5.0 V-0 15.9 V-0 10.0 63％ V-0 9.9 62％ ×
Table 3a
The embodiment numbering Component
A B-1 B-2 B-3 B-4 B-5 C D E-1 E-2 F G-1 G-2 G-3 G-4
Real 17 59 24 7 10 0.5 0.5 0.5 - 0.5
Real 18 59 24 7 10 0.5 0.5 0.5 - 0.5
Real 19 59 24 7 10 0.5 0.5 0.5 - 0.5
Real 20 59 24 7 10 0.5 0.5 0.2 0.5
Real 21 59 24 7 10 0.5 0.5 2.0 0.5
To 17 59 24 7 10 0.5 0.5 - 0.5
To 18 59 24 7 10 0.5 0.5 0.1 0.5
To 19 59 24 7 10 0.5 0.5 3.0 0.5
Real 22 59 24 7 10 0.5 0.5 0.5 0.5
Real 23 59 24 7 10 0.5 0.5 0.5 0.5
To 20 81 13 6 - 0.5 0.5 0.5 0.5
To 21 81 13 6 - 0.5 0.5 0.5 0.5
Table 3b
Before the processing After the term UV exposure (1000 hours) After the hot-water soak (168 hours, 7 days) The final evaluation
1/32 inch of flame retardant resistance Tensile impact strength 1/32 inch of flame retardant resistance Tensile impact strength Tensile impact strength keeps 1/32 inch of flame retardant resistance Tensile impact strength Tensile impact strength keeps
Real 17 V-0 17.5 V-0 15.6 89％ V-0 13.5 77％ fl
Real 18 V-0 16.8 V-0 17.1 102％ V-0 13.8 82％ f1
Real 19 V-0 16.4 V-0 15.3 93％ V-0 13.5 82％ f1
Real 20 V-0 16.2 V-0 15.9 98％ V-0 12.4 77％ f1
Real 21 V-0 17.4 V-0 16.7 96％ V-0 16.9 97％ f1
To 17 V-2 15.3 V-2 14.2 93％ V-2 13.5 88％ ×
To 18 V-2 19.5 V-2 17.4 89％ V-2 14.9 76％ ×
To 19 V-0 17.5 V-0 15.6 89％ V-0 11.4 65％ f2
Real 22 V-0 18.4 V-0 17.3 94％ V-0 15.2 83％ f1
Real 23 V-0 16.8 V-0 13.4 80％ V-0 12.8 76％ f1
To 20 V-0 32.6 V-2 20.1 62％ V-2 25.0 77％ f2
To 21 V-0 37.4 V-2 21.4 57％ V-2 27.1 72％ f2
Note:
Component (A): acrylic resin [HJ400, Samsung General Chemicals company]
Component (B)-1: high-melting-point halogen-based flame retardant, two pentabromobenzene oxidative ethanes [S-8010, Albemarle company, the U.S.]
Component (B)-2: high-melting-point halogen-based flame retardant, decabromodiphynly oxide [S-102E, Albemarle company, the U.S.]
Component (B)-3: high-melting-point halogen-based flame retardant
Component (B)-4: low melting point halogen-based flame retardant, tetrabromo-bisphenol-two (2,3 dibromopropyl ether) [PE68, Great Lakes, the U.S.]
Component (B)-5: low melting point halogen-based flame retardant, tetrabromo-bisphenol s type [Nonnen 52, MarubishiChemical, Japan]
Component (C): three ANTIMONY TRIOXIDE SB 203 99.8 PCT [SW, Ilsung Antimony company limited, Korea S]
Component (D): mineral filler, talcum [KCM 6300, KOCH]
Component (E)-1: uv-absorbing agent [Tinuvin 326, CIBA GEIGY]
Component (E)-2:HALS base UV stabilizer [Chimabsorber 944FD, CIBA GEIGY]
Component (F): particulate tetrafluoroethylene polymer [Teflon 800J, Dupont]
Component (G)-1: linking agent, pentaerythritol triacrylate [A-TMM-3L, Nippon Chemical, Japan]
Component (G)-2: linking agent, tetramethylol methane tetraacrylate [3-MM-T, Nippon Chemical, Japan]
Component (G)-3: linking agent, tetramethylolmethane three (3-mercaptopropionic acid ester) [PET-3-MP, Bruno BockChemical, Germany]
Component (G)-4: linking agent, trimethylolpropane acrylates [ATMPTMA, NipponChemical, Japan]
Though by above-mentioned preferred implementation the present invention is set forth, obviously can under the situation that does not deviate from disclosed scope of the present invention of claim and essence, can do various modifications, interpolation and alternative to those skilled in the art.

Claims (8)

1. flame retardant polypropylene resin composition, it comprises:
(A) melt flow index of 37-67 weight % is/10 minutes a acrylic resin of 4-40 gram;
(B) the high-melting-point halogen-based flame retardant of 17-29 weight %;
(C) weisspiessglanz of the white powder of 4-14 weight %;
(D) mineral filler of 2-22 weight %;
(E) UV stabilizer of 0.35-4.0 weight %;
(F) particulate tetrafluoroethylene polymer of 0.15-2.5 weight %; With
(G) linking agent of 0.08-3.5 weight %.
2. composition according to claim 1, wherein, described acrylic resin is homopolymer polypropylene or crystalline copolymer.
3. composition according to claim 1, wherein, described high-melting-point halogen-based flame retardant is decabromodiphynly oxide, ethene-two (tetrabromo phthalimide), two pentabromobenzene oxidative ethane or their mixture.
4. composition according to claim 1, wherein, described weisspiessglanz is ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide or their mixture.
5. composition according to claim 1, wherein, described mineral filler is talcum, barium sulfate, lime carbonate or their mixture.
6. composition according to claim 1, wherein, described UV stabilizer is that molecular weight is 2000 or the higher uv-absorbing agent and the composition of HALS based stabilizer.
7. composition according to claim 1, wherein, the fluorine content of described particulate tetrafluoroethylene polymer is 65-76 weight %.
8. composition according to claim 1, wherein, described linking agent is cyanacrylate, (two) ethylene glycol bisthioglycolate (methyl) acrylate, trimethylolpropane tris (methyl) acrylate or tetramethylolmethane (methyl) acrylate, Viscoat 295, Viscoat 295, pentaerythritol triacrylate, tetramethylol methane tetraacrylate or their mixture.
CNB2004800022503A 2003-01-15 2004-01-15 Flame retardant polypropylene resin composition with excellent weatherability Expired - Lifetime CN100336858C (en)

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