CN102417708A - Halogen-free flame-retardant polycarbonate composition for LED lampshade and preparation method and application thereof - Google Patents
Halogen-free flame-retardant polycarbonate composition for LED lampshade and preparation method and application thereof Download PDFInfo
- Publication number
- CN102417708A CN102417708A CN2011103753165A CN201110375316A CN102417708A CN 102417708 A CN102417708 A CN 102417708A CN 2011103753165 A CN2011103753165 A CN 2011103753165A CN 201110375316 A CN201110375316 A CN 201110375316A CN 102417708 A CN102417708 A CN 102417708A
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- CN
- China
- Prior art keywords
- retardant
- silicon
- led lampshade
- free flame
- polycarbonate
- Prior art date
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 96
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 69
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 68
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002210 silicon-based material Substances 0.000 claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 21
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 21
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- 238000002834 transmittance Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 150000003871 sulfonates Chemical class 0.000 claims description 17
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
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- 238000009792 diffusion process Methods 0.000 claims description 4
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- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 3
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- 238000005516 engineering process Methods 0.000 description 4
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- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229940125846 compound 25 Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical class CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004761 fibrosis Effects 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229960004692 perflenapent Drugs 0.000 description 1
- NJCBUSHGCBERSK-UHFFFAOYSA-N perfluoropentane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F NJCBUSHGCBERSK-UHFFFAOYSA-N 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a halogen-free flame-retardant polycarbonate composition for an LED lampshade, and a preparation method and application thereof, wherein the composition is prepared from the following components in percentage by mass: 89.8 to 99.79 percent of polycarbonate resin, 0.01 to 0.5 percent of sulfonate flame retardant, 0.1 to 5 percent of silicon-containing compound and 0.1 to 5 percent of additive. The invention adopts spherical or sphere-like silicon-containing compound with high heat resistance as the flame retardant, and the flame retardant keeps the original physical form no matter the polycarbonate is in a solidified or molten state, thus not only not hindering the catalytic flame retardance of the contact of the sulfonate flame retardant and the PC matrix, but also playing the role of synergistic flame retardance and light scattering. Therefore, the silicon-containing compound has two functions simultaneously, not only improves the flame retardant property, but also improves the light transmittance of the material, so that the final material meets the practical application requirement of the LED lampshade.
Description
Technical field
The present invention relates to LED illumination and macromolecule modified field of materials, be specifically related to a kind of LED lampshade with halogen-free flame-retardant polycarbonate composition and preparation method thereof and application with light.
Background technology
Polycarbonate (PC) is a kind of engineering plastics with excellent physical strength, resistance toheat, dimensional stability and high transmission rate.Be more suitable for as throwing light on and showing base material than existing transparent styrenic, acrylics with photodiffusion material.
Along with the fast development of LED technology, the application of polycarbonate in illumination and demonstration industry more and more widely.But, have the characteristics of high brightness, so its illumination range is narrow and can the dazzle effect be arranged to human eye because led light source belongs to pointolite.Present most popular method is to adopt the lampshade with light, makes pointolite become area source, thereby obtains evenly soft illuminating effect.From security consideration to light fixture; Flame retardant resistance requirement to the light fixture material therefor is also increasingly high, and particularly European Union not only requires the test through UL94V-0; And to meet the environmental requirement of Halogen, therefore research and development and the production to this material is a very big challenge.
In the prior art, in order to give polycarbonate scattering of light character, use will have the polymkeric substance of different refractivity or inorganic particulate joins the thermoplastic resin of external phase as disperse phase method.Also can realize required scattering of light property through the difference of the specific refractory power between adjusting disperse phase and the external phase or the particle diameter of disperse phase.Existing light scattering agent is divided into mineral-type and organic polymer class, and wherein organic polymer class light scattering agent has good, little to the material transmittance influence advantage of dispersion effect, replaces the mineral-type light scattering agent gradually.
Organic polymer class light scattering agent mainly is divided into hud typed esters of acrylic acid and silicone based at present.The crosslinked PMMA microballoon MBX-5/MBX-8/MBX-12 that for example Japanese SEKISUI company produces; Japan Shin-Etsu company produces organosilicon microballoon KMP-590.
In existing halogen-free and flame-retardant polycarbonate technology, mainly adopt Sulfonates fire retardant, phosphoric acid ester fire retardant and silicone based flame retardant.Wherein the phosphoric acid ester fire retardant is bigger to polycarbonate mechanical property and resistance toheat infringement, and the silicone based flame retardant flame retarding efficiency is not high, and bigger to the transmittance influence of scattering of light polycarbonate, though therefore existing patent report, practical application property is not high.
The sulphonate fire retardant is because addition is little, and is all very little to mechanical property and the transmittance influence of PC, is the present fire-retardant based flame retardant of the most suitable clear polycarbonate; But it also has and is difficult to make PC to reach the fire-retardant shortcoming of thin-walled, makes the polycarbonate that adopts this fire retardant be difficult to satisfy the requirement of product thin-walled property.
In order to make polycarbonate reach the fire-retardant rank of the following UL94V-0 of 2.0mm, mainly adopt the composite method of two or more fire retardant to realize at present, for example CN101906244A adopts sulphonate fire retardant and the composite 1.6mmV-0 that reaches of silicone based flame retardant.Yet adopting the maximum shortcoming of this method is that light transmission with expendable material is a cost, therefore is difficult to reach the desired high scattering of LED lampshade material (mist degree is greater than 95%), high printing opacity (transmittance is greater than 80%), high heat-resisting (pressing test through 125 degree balls) and halogen-free flameproof.
The inventor herein also finds through analysis and research and experimental verification; With sulphonate fire retardant compound system in; Adopt the organic silicon fibre retardant of linear or partial cross-linked molecular structure, not only can damage the flame retardant properties of material, and to the transmittance significant adverse of material.Because the sulphonate fire retardant only has the catalysis flame retardant effect to polycarbonate; And the organic silicon fibre retardant macromolecular chain of linear or partial cross-linked molecular structure is dispersed in the polycarbonate matrix easily p-sulfonic acid salt fire retardant and plays and intercept and the coating effect, thereby makes its " inefficacy "; In addition, the refractive index difference of the organosilicon of linear structure itself and PC and be prone to the property separated out causes it to transmittance influence of material significantly.
Summary of the invention
For the shortcoming and deficiency that overcome prior art, primary and foremost purpose of the present invention is to provide a kind of LED lampshade to use halogen-free flame-retardant polycarbonate composition.
Another object of the present invention is to provide the preparation method of above-mentioned LED lampshade with halogen-free flame-retardant polycarbonate composition.
A purpose more of the present invention is to provide the purposes of above-mentioned LED lampshade with halogen-free flame-retardant polycarbonate composition.
The object of the invention is realized through following technical proposals:
A kind of LED lampshade is used halogen-free flame-retardant polycarbonate composition, is prepared by the composition of following mass percent:
Polycarbonate resin: 89.8～99.79%
Sulfonates fire retardant: 0.01～0.5%
Silicon-containing compound: 0.1～5%
Additive: 0.1～5%;
Preferably, a kind of LED lampshade is that composition by following mass percent prepares with halogen-free flame-retardant polycarbonate composition:
Polycarbonate resin: 91.7～99.72%
Sulfonates fire retardant: 0.08～0.3%
Silicon-containing compound: 0.1～3%
Additive: 0.1～5%;
Particularly preferably, a kind of LED lampshade is that composition by following mass percent prepares with halogen-free flame-retardant polycarbonate composition:
Polycarbonate resin: 93.3～99.70%
Sulfonates fire retardant: 0.1～0.2%
Silicon-containing compound: 0.1～1.5%
Additive: 0.1～5%.
The transmittance of said polycarbonate resin >=88% (pressing ASTM D1003 standard testing, thickness 2mm) if be lower than the light transmission that this transmittance will influence the scattering of light PC material of preparation, thereby can reduce the light efficiency of whole LED optics;
Described polycarbonate resin is an aromatic polycarbonate resin well known to those skilled in the art, comprises homo-polycarbonate, Copolycarbonate and thermoplastic polyester carbonic ether, preferred homo-polycarbonate;
Described homo-polycarbonate preferable weight-average molecular weight M
WBe 12000～40000 homo-polycarbonate, special preferable weight-average molecular weight M
WIt is 20000～30000 homo-polycarbonate.The weight-average molecular weight M here
WAll be to confirm with respect to the measurement of BPA polycarbonate standard specimen.As weight-average molecular weight M
WBe lower than at 12000 o'clock, because molecular weight is too low, cause the mechanical property of materials not good, deterioration easily is not suitable for being used for doing the matrix of light-scattering material; And weight-average molecular weight M
WAfter being higher than 40000, the material melt viscosity is high, and it is mobile poor to cause, and is difficult for processing, is unfavorable for the dispersion of various additives, and the high-molecular weight polycarbonate since in building-up process easily because of part " implode " produces " brilliant point ", transmittance can reduce.Solve but also can use through the polycarbonate resin combination collocation of different molecular structures and molecular weight.
Described homo-polycarbonate is specifically preferred: Panlite L-1225WP, L-1250Y and L-1225L that Japanese TEIJIN company produces; U.S. SABIC company produces 121 and 141; Germany BAYER company produces 2805,2807; DOW company produces 201-5,301-10 and 301-22; Japan bright dipping TARFLONA2200, A1900 and A1700; Transmittance is all more than or equal to 88%.
Described Sulfonates fire retardant comprises fluorinated alkyl sulfonate, sulfobenzide sulphonate and diphenyl ether sulfonate;
The alkyl chain carbon number of said fluorinated alkyl sulfonate is 2～18, and is preferred 2～12, more preferably 2～8; The alkyl chain carbon number is that 2～8 fluorinated alkyl sulfonate has R 116 sulphonate, UN 2424 sulphonate, perfluorinated butane sulphonate, perflenapent sulphonate, PFH sulphonate or perfluoro octane sulfonate; Wherein preferred perfluorinated butane sulphonate, for example U.S. 3M produces potassium perfluorobutane sulfonate (FR2025);
Described sulfobenzide sulphonate and diphenyl ether sulfonate, the alkyl chain carbon number of the alkyl that connects on its molecular structure is 0～18, and is preferred 0～12, more preferably 0～6; Potassium diphenylsulfone sulfonate (KSS) for example;
Metal in the described Sulfonates fire retardant is more than one in basic metal (lithium Li, sodium Na, potassium K, rubidium Rb, caesium Cs) salt or earth alkali metal (beryllium Be, magnesium Mg, calcium Ca, strontium Sr, the barium Ba) salt, preferred as alkali.
Described silicon-containing compound is for the mixture of at least two kinds the spherical or type spherical solid-state silicon-containing compound with high thermal stability, even in the polycarbonate matrix of high-temperature fusion, also keep original physical aspect; Particle diameter is 0.1～10 μ m, and preferable particle size is the silicon-containing compound of 0.5～8 μ m; Most preferably particle diameter is the silicon-containing compound of 1～5 μ m.If particle diameter is lower than 0.1 μ m or is higher than 10 μ m, then dispersion effect and transmittance all can reduce.
Described silicon-containing compound is silicoorganic compound or inorganic silicon compound.
Described silicoorganic compound are cross-linking type siloxane oligomer or cross-linking type siloxane polymer, preferred powder-type silicone resin, organic poly sesquisiloxane or poly organic silicon boroxane; Its side group can be more than one in methyl, vinyl, phenyl, hydroxyl or the methoxyl group.In order to guarantee flame retardant effect, the molar content of phenyl is not less than 40% in the side group.
The silicoorganic compound microballoon can be the single or multiple lift nucleocapsid structure.
The compound method of powder-type silicone resin, organic poly sesquisiloxane and poly organic silicon boroxane is not limit.
The powder-type silicone resin can form through polycondensation through organosilyl monobasic, binary, ternary and quaternary monomer, the polymerization of polymerization method preferred emulsion; Preferred examples such as U.S. MOMENTIVE TOSPEARL 120 and Japanese Shin-Etsu KMP-590, both are interlink molecular structure, spheroidal particle, median size 2 μ m.
Organic poly sesquisiloxane can form through polycondensation through organosilyl monobasic, binary and ternary monomer, the polymerization of polymerization method preferred emulsion; Concrete grammar can be with reference to Chinese patent 200510033478.5.
The compound method of organic poly sesquisiloxane APS is following:
In the 250ml there-necked flask, add 100ml water, 0.8g sodium lauryl sulphate, 0.8ml TMAH (the 25% volumetric molar concentration aqueous solution); With 8ml aminopropyl triethoxysilane (more than 98%, industrial goods) and 16ml phenyl triethoxysilane (more than 98%, industrial goods); After mixing, drip from tap funnel under stirring, 120min adds; Continuing reaction stops after 8 hours stirring; Spinning again after spinning, gained white precipitate are washed with water-dispersion gets white micro mist product after the drying.
The poly organic silicon boroxane can obtain through ternary monomer and organosilyl monobasic, binary and the common polycondensation of ternary monomer of boric acid or organic boron; Concrete compound method can be with reference to Chinese patent 200610123965.5 and CN101033330A.
The compound method of poly organic silicon boroxane SBM-01 is following:
In the dry four-hole boiling flask that mechanical stirring, water trap nuclear condensing surface, nitrogen conduit are housed; Feed drying nitrogen; Eliminate the air in the flask; Add then after 6.2g boric acid, 44.0g phenylbenzene dihydroxyl silane, 29.6g dimethyldiethoxysilane, 29.6g vinyltrimethoxy silane and 250ml dry toluene stir, be warming up to 110 ℃ of backflow 4h gradually and remove toluene and get the organic silicon-boron prepolymer; This 100 weight part prepolymer and 1 weight part X 2073 and 400 weight part zero(ppm) water are fully stirred form homodisperse emulsion; As seed, add 1 weight part initiator potassium persulfate (KPS), drip 70 parts by weight of methylmethacrylate (MMA), add ammoniacal liquor behind the constant temperature polymerization 8h and be adjusted to neutrality; With the poly organic silicon boron cpd SBM-01 that obtains nucleocapsid structure behind saturated potassium chloride solution breakdown of emulsion, filtration, washing, drying, the crushing screening, organic silicon-boron nuclear content 60wt%, wherein side group phenyl molar content 40%.
The compound method of poly organic silicon boroxane SBM-02 is following:
In the dry four-hole boiling flask that mechanical stirring, water trap nuclear condensing surface, nitrogen conduit are housed; Feed drying nitrogen; Eliminate the air in the flask; Add then after 6.2g boric acid, 87.0g phenylbenzene dihydroxyl silane, 7.5g dimethyldiethoxysilane, 15.0g vinyltrimethoxy silane and 250ml dry toluene stir, be warming up to 110 ℃ of backflow 4h gradually and remove toluene and get the organic silicon-boron prepolymer; This 100 weight part prepolymer and 1 weight part X 2073 and 400 weight part zero(ppm) water are fully stirred form homodisperse emulsion; As seed, add 1 weight part initiator potassium persulfate (KPS), drip 18 parts by weight of methylmethacrylate (MMA), add ammoniacal liquor behind the constant temperature polymerization 8h and be adjusted to neutrality; With the poly organic silicon boron cpd SBM-02 that obtains nucleocapsid structure behind saturated potassium chloride solution breakdown of emulsion, filtration, washing, drying, the crushing screening, its organosilicon nuclear content 85wt%, wherein side group phenyl molar content 80%.
Described inorganic silicon compound comprises oxide compound, carbide, nitride and the silicate etc. of silicon; Specific examples such as silicon-dioxide, silit, silicon nitride, quartz, granulated glass sphere, kaolin, wollastonite, molecular sieve; Wherein preferred preparing spherical SiO 2 particles is about the preferred 2 μ m of median size.
Inorganic silicon compound can adopt all kinds of surface treatment agents to carry out surface treatment, to improve the consistency of itself and matrix resin; Described surface treatment agent is silane coupling agent, titanate coupling agent or aluminate coupling agent, wherein the preferred silane coupling agent.
Described silicon-containing compound is prerequisite by two or more composition the in silicoorganic compound or the inorganic silicon compound with the salient features that does not influence material.
LED lampshade of the present invention can also contain additive with halogen-free flame-retardant polycarbonate composition; Content of additive is 0.1～5%, and the concrete kind and the addition of additive are: oxidation inhibitor 0.1～1.2%, anti-dripping agent 0～0.6%, releasing agent 0～1.0%, weather resisting agent 0～2.0%, staining agent 0～0.1%, white dyes 0～0.1%;
Preferably, the concrete kind of additive and addition are: oxidation inhibitor 0.1～1.0%, anti-dripping agent 0～0.4%, releasing agent 0～0.6%, weather resisting agent 0～2.0%, staining agent 0～0.1%, white dyes 0～0.05%;
More preferably, the concrete kind of additive and addition are: oxidation inhibitor 0.1～0.6%, anti-dripping agent 0～0.2%, releasing agent 0～0.3%, weather resisting agent 0～1.0%, staining agent 0.001～0.1%, white dyes 0～0.01%;
Described per-cent is to account for the per-cent of LED lampshade with halogen-free flame-retardant polycarbonate composition raw material total mass.
The thermolysis starting temperature of described oxidation inhibitor, anti-dripping agent, releasing agent, weather resisting agent, staining agent and white dyes all is greater than or equals 260 ℃.The thermolysis starting temperature is material weightless temperature that was reached in 1% o'clock under nitrogen atmosphere.
Described oxidation inhibitor is made up of primary antioxidant and auxiliary antioxidant, and both mass ratioes are 1: 5～5: 1, preferred 1: 3～3: 1.
Described primary antioxidant is phenols and/or amine; Preferred phenols; Preferred especially season amylalcohol four (3-(3, the 5-di-tert-butyl)-4-hydroxybenzene (antioxidant 1010), octadecyl-3-(3,5-two uncles Ding-4-hydroxybenzene)-propionic ester (antioxidant 1076), N; N-normal hexane-1; The 6-dihydroxyl (3-(3,5-di-t-butyl-4-phenylor phenol acetic ester (oxidation inhibitor 1098), vinyl-two (ethenoxy group) two-(3-(5-tertiary butyl-4-hydroxy-tolyl)-propionic ester) (oxidation inhibitor 245) or 2,2 '-methylene bis (more than one in the 4-methyl-6-tert butyl phenol (antioxidant 2246).
Described auxiliary antioxidant is phosphorous acid esters auxiliary antioxidant and/or thioesters class auxiliary antioxidant;
Described phosphorous acid esters auxiliary antioxidant is three (2; The 4-di-tert-butyl-phenyl) phosphorous acid ester (oxidation inhibitor 168), triphenyl phosphite (TPP), two (2; 6-two-tertiary butyl-4-tolyl) pentaerythritol phosphite (PEP-36), four (2; 4-two-trimethylphenylmethane base)-in 4,4 ' biphenyl-two phosphorus phosphorous acid ester (P-EPQ) or two (2,4-two withered phenyl) pentaerythritol phosphite (S9228) more than one;
Described thioesters class auxiliary antioxidant is in (412S) more than one of the two lauryl alcohol esters (DLTDP) of sulphur diethylammonium two [3-(3,5-di-t-butyl-4-hydroxybenzene) propionic ester] (oxidation inhibitor 1035), thio-2 acid, thio-2 acid stearyl alcohol ester (DSTDP) or tetramethylolmethane four (3-lauryl thiopropionate).
Described anti-dripping agent is the fluoropolymer resin with fibrosis ability, and its effect is to prevent that melts from producing drip effect in combustion processes;
Described anti-dripping agent preferably polytetrafluoroethylene and pvdf; More preferably surface cladding type tetrafluoroethylene, wherein the mass content of tetrafluoroethylene is 40～70%, preferred 50-60%; The too low then anti-drippage effect of the content of tetrafluoroethylene is relatively poor, too highly then is unfavorable for homodisperse in matrix resin.The surface coating can be acrylic polymer, styron, acrylonitritrile-styrene resin; Wherein preferred acrylonitritrile-styrene resin (SAN); Practical implementation is Mitsubishi A-3750 and A-3800 for example, and polytetrafluoroethylene content is about 50wt%.
The use of anti-dripping agent can reduce the transparency of material, therefore must require to confirm its addition according to reality.
Described releasing agent is organic silicone compounds, pentaerythritol tetrastearate (PETS), Zerol, montanic acid wax or other fatty acid ester compounds; Wherein preferred pentaerythritol tetrastearate (PETS) also can be with itself and other composite use of one or more releasing agents.
Described weather resisting agent is hindered amine light stabilizer (HALS) and/or UV light absorber;
Described hindered amine light stabilizer (HALS) is two (2,2,6,6 ,-tetramethyl pyridine base) sebates (TINUVIN 770), gather-{ 6-[(1; 1,3, the 3-tetramethyl butyl)-amido]-1,3,5-triazines-2; 4-two bases] [(2,2,6, the 6-tetramethyl-piperidyl)-imino--hexa-methylene-[4-(2,2 for 2-; 6,6-tetramethyl-piperidyl)-imino-]] (944) or gather [1-(2 '-hydroxyethyl)-2,2,6,6-tetramethyl--4 hydroxy piperidine succinate] (622).
Described UV light absorber is benzotriazole category UV light absorber, benzophenone UV light absorber or Whitfield's ointment ester group UV light absorber.
Described benzotriazole category UV light absorber is a 2-(2-hydroxyl-3; 5-two (1,1-dimethyl--phenyl)-2H-benzotriazole (TINUVIN 234), 2-(2H-benzotriazole-2-yl)-4-(1,1; 3; The 3-tetramethyl butyl)-phenol (CYASORB 5411), 2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-5-benzotriazole (UV-P) or 2,2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole (UV-327);
Described UVNUL MS-40 base UV light absorber is UV-531 (UV-531);
Described Whitfield's ointment ester group UV light absorber is that salol, Whitfield's ointment are to butyl phenyl ester or p-octylphenyl salicylate.
Other UV light absorber also has 1,3-two [(2-cyanic acid-3,3-biphenyl acryl) oxygen base]-2,2-two [[(2-cyanic acid-3,3-biphenyl acryl) oxygen base] methyl] propane (UVINUL 3030).
The preferred benzotriazole category UV light absorber of described weather resisting agent also can be with itself and other composite use of one or more UV light absorbers.
Described staining agent is all kinds of inorganic or organic pigment and dyestuff.The adding of staining agent is a prerequisite with the not obvious each item performance that influences polycarbonate compositions.
In addition, the inventor herein finds, uses a spot of white dyes can reduce the yellow value degree of material, and material is bleached, and can further increase the brightness value of LED lamp simultaneously.The addition of white dyes most preferably is 0.001～0.03wt%.Described white dyes is two benzoxazoles, phenyl tonka bean camphor or bis-styrylbiphenyl type white dyes, for example the Uvitex OB of Ciba product.
Above-mentioned LED lampshade can adopt a step extrusion by melting with the preparation method of halogen-free flame-retardant polycarbonate composition, specifically may further comprise the steps:
Polycarbonate resin, Sulfonates fire retardant, silicon-containing compound and additive are mixed; With mixture drop into fusion in the forcing machine, extrude, granulation, obtain the LED lampshade and use halogen-free flame-retardant polycarbonate composition; Extrusion temperature is 230～280 ℃.
Above-mentioned LED lampshade can also adopt two step extrusion by meltings with the preparation method of halogen-free flame-retardant polycarbonate composition, specifically comprises the steps:
(1) getting X multiple proportions routine Sulfonates fire retardant, silicon-containing compound and additive and polycarbonate resin mixes; With mixture drop into fusion in the forcing machine, extrude, granulation, obtain light diffusion fire-retardant polycarbonate master batch;
(2) master batch of getting 1 weight part step (1) mixes with the polycarbonate resin of (X-1) weight part; With mixture drop into fusion in the forcing machine, extrude, granulation, obtain the LED lampshade and use halogen-free flame-retardant polycarbonate composition;
Said X is 1～10;
Extrusion temperature in step (1) and (2) is 230～280 ℃.
Above-mentioned LED lampshade has no particular limits equipment with the preparation method of halogen-free flame-retardant polycarbonate composition.For example, can adopt single screw rod or twin screw extruder to melt extrude.But, preferentially adopt the better double screw extrusion method of dispersion effect in order to guarantee the dispersing uniformity of each component of compsn.
The not special restriction of the forming method of the polycarbonate compositions that makes according to the present invention; Available existing forming technique commonly used, for example injection molding method, extrusion moulding, rolling process, blow moulding, vacuum forming, press molding method, foam-formed method and other technologies.
Above-mentioned LED lampshade can be used to make the LED lampshade with halogen-free flame-retardant polycarbonate composition.
The present invention has following advantage and effect with respect to prior art:
The present invention adopts has high heat-stable sphere or type spheric silicon-containing compound as fire retardant; This fire retardant is no matter polycarbonate all keeps original physical aspect when curing or molten state; The contact catalysis that so neither hinders sulphonate fire retardant and PC matrix is fire-retardant, plays a part cooperative flame retardant and scattering of light again.Therefore this silicon-containing compound has been taken into account two kinds of functions simultaneously, has both improved flame retardant properties, has improved the light transmission of material again, thereby has made final material reach the application request of LED lampshade.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Comparative Examples 1～6 is by step extrusion by melting preparation: promptly press table 1 and fill a prescription raw materials mix, then with mixture drop into fusion in the forcing machine, extrude, granulation, obtain the compsn pellet; Extrusion temperature is 250 ℃.
Embodiment 1～10 is by step extrusion by melting preparation: the prescription of promptly pressing table 2 and table 3 is raw materials mix, then with mixture drop into fusion in the forcing machine, extrude, granulation, obtain the LED lampshade and use halogen-free flame-retardant polycarbonate composition; Extrusion temperature is 250 ℃.
Embodiment 11～14 prepares by two step extrusion by meltings:
(1) Sulfonates fire retardant, silicon-containing compound and additive and the polycarbonate resin with 5 times of table 3 formula rates mixes (with embodiment 14 is example, and the per-cent of this step raw material total mass of each ingredients constitute is: Sulfonates fire retardant 1%, silicon-containing compound 25%, additive 25%, polycarbonate resin 49%); With mixture drop into fusion in the forcing machine, extrude, granulation, obtain light diffusion fire-retardant polycarbonate master batch;
(2) master batch of getting 20 weight part steps (1) then mix with 80 weight part polycarbonates after the oven dry again through melt extruding, pelletizing gets the LED lampshade and uses halogen-free flame-retardant polycarbonate composition;
Extrusion temperature in step (1) and (2) is 250 ℃.
The organic poly sesquisiloxane APS that table 2 and table 3 adopted is prepared by following method:
In the 250ml there-necked flask, add 100ml water, 0.8g sodium lauryl sulphate, 0.8ml TMAH (the 25% volumetric molar concentration aqueous solution); After 8ml aminopropyl triethoxysilane (more than 98%, industrial goods) and 16ml phenyl triethoxysilane (more than 98%, industrial goods) mixed; Stir down and drip from tap funnel; 120min adds, and continues reaction and stops after 8 hours stirring spinning; Spinning again after the gained white precipitate washs with water-dispersion gets white micro mist product after the drying.
The poly organic silicon boroxane SBM-01 that table 2 and table 3 adopted is prepared by following method:
In the dry four-hole boiling flask that mechanical stirring, water trap nuclear condensing surface, nitrogen conduit are housed; Feed drying nitrogen; Eliminate the air in the flask; Add then after 6.2g boric acid, 44.0g phenylbenzene dihydroxyl silane, 29.6g dimethyldiethoxysilane, 29.6g vinyltrimethoxy silane and 250ml dry toluene stir, be warming up to 110 ℃ of backflow 4h gradually and remove toluene and get the organic silicon-boron prepolymer; This 100 weight part prepolymer and 1 weight part X 2073 and 400 weight part zero(ppm) water are fully stirred form homodisperse emulsion; As seed, add 1 weight part initiator potassium persulfate (KPS), drip 70 parts by weight of methylmethacrylate (MMA), add ammoniacal liquor behind the constant temperature polymerization 8h and be adjusted to neutrality; With the poly organic silicon boron cpd SBM-01 that obtains nucleocapsid structure behind saturated potassium chloride solution breakdown of emulsion, filtration, washing, drying, the crushing screening, organic silicon-boron nuclear content 60wt%, wherein side group phenyl molar content 40%.
The poly organic silicon boroxane SBM-02 that table 2 and table 3 adopted is prepared by following method:
In the dry four-hole boiling flask that mechanical stirring, water trap nuclear condensing surface, nitrogen conduit are housed; Feed drying nitrogen; Eliminate the air in the flask; Add then after 6.2g boric acid, 87.0g phenylbenzene dihydroxyl silane, 7.5g dimethyldiethoxysilane, 15.0g vinyltrimethoxy silane and 250ml dry toluene stir, be warming up to 110 ℃ of backflow 4h gradually and remove toluene and get the organic silicon-boron prepolymer; This 100 weight part prepolymer and 1 weight part X 2073 and 400 weight part zero(ppm) water are fully stirred form homodisperse emulsion; As seed, add 1 weight part initiator potassium persulfate (KPS), drip 18 parts by weight of methylmethacrylate (MMA), add ammoniacal liquor behind the constant temperature polymerization 8h and be adjusted to neutrality; With the poly organic silicon boron cpd SBM-02 that obtains nucleocapsid structure behind saturated potassium chloride solution breakdown of emulsion, filtration, washing, drying, the crushing screening, its organosilicon nuclear content 85wt%, wherein side group phenyl molar content 80%.
Comparative Examples 1～6 and embodiment 1～14 resulting composition pellet is dull and stereotyped through 120 ℃ of dryings are injection molded into standard bar and long 100mm * wide 80mm * thick 2.0mm under 280 ℃ of temperature after 4 hours light face, and the mould temperature control is at 100 ℃.
Mechanical property is according to the ASTM standard testing, and flame retardant properties is according to the UL94 standard testing, and ball impression temperature (Ball Pressure Test) and glow wire test (GWFI) are respectively according to IEC60695-10-2 and IEC60695-2-12 test.The test of transmittance and mist degree: light face flat board that will long 100mm * wide 80mm * thick 2.0mm is tested by ASTM D1003 standard, and the test light wavelength region is at 380～780nm.
Test result is shown in table 4-6.
The composition of raw materials of each Comparative Examples of table 1 (weight percent)
The composition of raw materials (weight percent) of table 2 embodiment 1-7
The composition of raw materials (weight percent) of table 3 embodiment 8-14
The The performance test results of each Comparative Examples products obtained therefrom of table 4
The The performance test results of table 5 embodiment 1-7 products obtained therefrom
The The performance test results of table 6 embodiment 8-14 products obtained therefrom
Can find out that by Comparative Examples 1-3 the composite use flame retardant properties of sulphonate fire retardant and single silicone resin is not good enough, can improve the anti-drippage performance of material though add tetrafluoroethylene, thereby improve fire-retardant rank, very big to the transmittance influence of material; See from Comparative Examples 4-6 test result; The ZGK 5 that adopts linearity molecular structure and sulphonate fire retardant are composite not to have help basically to fire-retardant, can cause material in the combustion testing process, to produce " self-extinguishing time prolongation ", " promotion molten drop deposits yields " and " side burning " phenomenon on the contrary.
And see that from embodiment 1-7 gained test result adopt cross-linking organosilicon compound microballoon or inorganic silicon compound microballoon all to produce good cooperative flame retardant effect with the sulphonate fire retardant, the flame retardant rating of material obviously improves; Then can further improve " molten drop " phenomenon of material like the tetrafluoroethylene (embodiment 9-14) of matched with proper, thereby make material reach more minimal thickness UL94V-0 rank.
In addition, can find, adopt linear polysiloxane (Comparative Examples 4-6) can obviously influence the light transmission of material from full light transmittance data; And employing silicon-containing compound microballoon (embodiment 1-14) has not only played the effect of light diffusion, and less to the light transmission influence of material, more meets the application request of LED lampshade.
In sum; The flame retardant polycarbonate composition that adopts silicon-containing compound microballoon and sulphonate fire retardant compound system to obtain has favorable mechanical performance, flame retardant properties, resistance toheat and light transmission; Be suitable for injection moulding, extrude with roll into each in the LED lampshade of shape, this lampshade has been taken into account light transmission and light scattering effect.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a LED lampshade is used halogen-free flame-retardant polycarbonate composition, it is characterized in that: be that composition by following mass percent prepares:
Polycarbonate resin: 89.8～99.79%
Sulfonates fire retardant: 0.01～0.5%
Silicon-containing compound: 0.1～5%
Additive: 0.1～5%;
Described silicon-containing compound is the mixture of at least two kinds the spherical or type spherical solid-state silicon-containing compound with high thermal stability, and its particle diameter is 0.1～10 μ m.
2. LED lampshade according to claim 1 is used halogen-free flame-retardant polycarbonate composition, it is characterized in that: be that composition by following mass percent prepares:
Polycarbonate resin: 91.7～99.72%
Sulfonates fire retardant: 0.08～0.3%
Silicon-containing compound: 0.1～3%
Additive: 0.1～5%.
3. LED lampshade according to claim 1 is used halogen-free flame-retardant polycarbonate composition, it is characterized in that: be that composition by following mass percent prepares:
Polycarbonate resin: 93.3～99.70%
Sulfonates fire retardant: 0.1～0.2%
Silicon-containing compound: 0.1～1.5%
Additive: 0.1～5%.
4. LED lampshade according to claim 1 is used halogen-free flame-retardant polycarbonate composition, it is characterized in that:
Described polycarbonate resin is a kind of in homo-polycarbonate, Copolycarbonate or the thermoplastic polyester carbonic ether, and its weight-average molecular weight is 12000～40000, its transmittance >=88%;
Described Sulfonates fire retardant is more than one in fluorinated alkyl sulfonate, sulfobenzide sulphonate or the diphenyl ether sulfonate.
5. LED lampshade according to claim 1 is used halogen-free flame-retardant polycarbonate composition, it is characterized in that:
Described polycarbonate resin is a homo-polycarbonate, and its weight-average molecular weight is 20000～30000, its transmittance >=88%;
Described Sulfonates fire retardant is potassium perfluorobutane sulfonate and potassium diphenylsulfone sulfonate;
Described silicon-containing compound is two or more in powder-type silicone resin, organic poly sesquisiloxane, poly organic silicon boroxane or the silicon-dioxide.
6. LED lampshade according to claim 5 is used halogen-free flame-retardant polycarbonate composition, it is characterized in that:
Described powder-type silicone resin, organic poly sesquisiloxane and poly organic silicon boroxane, the molar content of phenyl is not less than 40% in the side group;
The particle diameter of said silicon-dioxide is 2 μ m.
7. LED lampshade according to claim 1 is used halogen-free flame-retardant polycarbonate composition, it is characterized in that: described additive is two or more in oxidation inhibitor, anti-dripping agent, releasing agent, weather resisting agent, staining agent or the white dyes; Thermolysis starting temperature >=260 of said additive ℃.
8. each described LED lampshade of claim 1-7 is characterized in that may further comprise the steps: polycarbonate resin, Sulfonates fire retardant, silicon-containing compound and additive are mixed with the preparation method of halogen-free flame-retardant polycarbonate composition; With mixture drop into fusion in the forcing machine, extrude, granulation, obtain the LED lampshade and use halogen-free flame-retardant polycarbonate composition.
9. each described LED lampshade of claim 1-7 is characterized in that may further comprise the steps with the preparation method of halogen-free flame-retardant polycarbonate composition:
(1) get X times of claim 1-7 in each Sulfonates fire retardant, silicon-containing compound and additive and polycarbonate resin of mass percent mix; With mixture drop into fusion in the forcing machine, extrude, granulation, obtain light diffusion fire-retardant polycarbonate master batch;
(2) master batch of getting 1 weight part step (1) mixes with the polycarbonate resin of (X-1) weight part; With mixture drop into fusion in the forcing machine, extrude, granulation, obtain the LED lampshade and use halogen-free flame-retardant polycarbonate composition;
Said X is 1～10.
10. each described LED lampshade of claim 1-7 is with the application of halogen-free flame-retardant polycarbonate composition in making the LED lampshade.
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| CN110577728A (en) * | 2018-06-07 | 2019-12-17 | 江苏金发科技新材料有限公司 | polycarbonate composition with high ball pressure temperature and solvent resistance and preparation method thereof |
| CN111087783A (en) * | 2019-12-12 | 2020-05-01 | 上海普利特复合材料股份有限公司 | Transparent halogen-free flame-retardant PC material capable of being used for UV adhesive curing and preparation method thereof |
| CN111019316A (en) * | 2019-12-26 | 2020-04-17 | 陈志强 | Polycarbonate composition with light diffusion performance, preparation method and application |
| CN111040173A (en) * | 2019-12-26 | 2020-04-21 | 陈志强 | Preparation method and application of silicone rubber microsphere light diffusant |
| CN111381141A (en) * | 2019-12-31 | 2020-07-07 | 浙江凯耀照明有限责任公司 | System and method for rapidly judging mutual influence of performances of lamp filament and lamp shade |
| CN111381141B (en) * | 2019-12-31 | 2022-09-16 | 浙江凯耀照明有限责任公司 | System and method for rapidly judging mutual influence of performances of lamp filament and lamp shade |
| CN114957955A (en) * | 2022-05-17 | 2022-08-30 | 东莞市旺品实业有限公司 | High heat dissipation polycarbonate material and high heat dissipation PC wick |
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Application publication date: 20120418 |