CN1735653A - Method for making fire-retarded glass-filled polycarbonate and related compositions - Google Patents
Method for making fire-retarded glass-filled polycarbonate and related compositions Download PDFInfo
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- CN1735653A CN1735653A CN 200380108205 CN200380108205A CN1735653A CN 1735653 A CN1735653 A CN 1735653A CN 200380108205 CN200380108205 CN 200380108205 CN 200380108205 A CN200380108205 A CN 200380108205A CN 1735653 A CN1735653 A CN 1735653A
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- polycarbonate
- phosphorous
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- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 45
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 34
- 239000011521 glass Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000003063 flame retardant Substances 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 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 claims abstract description 12
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract 6
- 239000003112 inhibitor Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 14
- -1 alkali metal cation Chemical class 0.000 claims description 10
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- QTZBTBLHYPSFMG-UHFFFAOYSA-N 5-chloro-3-methylpyridin-2-amine Chemical compound CC1=CC(Cl)=CN=C1N QTZBTBLHYPSFMG-UHFFFAOYSA-N 0.000 claims description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 claims description 2
- NBQOXMJHMFFTHP-UHFFFAOYSA-N [F].P(O)(O)O Chemical compound [F].P(O)(O)O NBQOXMJHMFFTHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- UWETVEYENGVTQS-UHFFFAOYSA-N difluorophosphinous acid Chemical compound OP(F)F UWETVEYENGVTQS-UHFFFAOYSA-N 0.000 claims description 2
- 150000003009 phosphonic acids Chemical class 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims 1
- 229920005668 polycarbonate resin Polymers 0.000 abstract description 18
- 239000004431 polycarbonate resin Substances 0.000 abstract description 18
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 239000000155 melt Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 229910052700 potassium Inorganic materials 0.000 description 12
- 239000011591 potassium Substances 0.000 description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 239000003365 glass fiber Substances 0.000 description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 10
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical group [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009955 starching Methods 0.000 description 2
- 239000011145 styrene acrylonitrile resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FSUGBCUTECFUIL-UHFFFAOYSA-N [Na].FC(F)(F)C(F)(F)C(F)(F)F Chemical compound [Na].FC(F)(F)C(F)(F)C(F)(F)F FSUGBCUTECFUIL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000206 moulding compound Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical class OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- GGRIQDPLLHVRDU-UHFFFAOYSA-M potassium;2-(benzenesulfonyl)benzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1 GGRIQDPLLHVRDU-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- OEJPCMVOWZXTDT-UHFFFAOYSA-N sodium;tetrafluoromethane Chemical compound [Na].FC(F)(F)F OEJPCMVOWZXTDT-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
It has now been surprisingly found that addition of a phosphorous-containing oxy acid to a glass-filled polycarbonate composition substantially improves its fire retardant performance. Thus, the present invention provides a method for making a flame-retarded glass-filled polycarbonate resin comprising adding to the resin an effective flame-retardant amount of a phosphorous-containing oxy acid. Where appropriate, the melt strength of the polycarbonate is enhanced by the addition of an antidrip agent and the performance can be further enhanced by the addition of a flame retardant. Use of such a composition results in superior fire-retardant performance.
Description
Background technology
The application requires the U.S. Provisional Patent Application No.60/433 of submission on December 16th, 2002,740 right of priority, and it is incorporated herein as a reference.
The application relates to the method that the polycarbonate resin that glass is filled has flame retardant properties, relates to the composition that is used for this method, and passes through this class flame-retarded polycarbonate resin that this method is produced.
Because the intensity of the polycarbonate resin that glass is filled, it has very wide range of commercial purposes.They are particularly useful for the injection molding of thin wall component.Yet the polycarbonate resin self that glass is filled has combustibility and material can also melted by heat and drip, and causes that adjacent material catches fire.Therefore, for the polycarbonate that in a lot of the application, uses glass to fill safely, be necessary to comprise the additive that can stop material combustibility and/or reduce dropping liquid.Select to reach the additive of this purpose according to this consideration, this additive should not reduce the desired intensity characteristic, does not produce new problem (for example relevant with some halogenate additive potential environmental problem) and does not significantly improve price.
The multiple differing materials that is used to produce fire-retardant and/or dirp-proof polycarbonate composition has been described.At United States Patent(USP) Nos. 3,971, these examples of material have been described in 756,4,028,297,4,110,299,4,130,530,4,303,575,4,335,038,4,552,911,4,916,194,5,218,027 and 5,508,323.Though have various openly, still have the leeway of improving the poly carbonate resin composition prescription that fire-retardant glass fills.
Commercial these additives that are widely used in fire-retarded polycarbonate resin composition are organic salt, specifically sulfonate.The specific examples of these salt is a fluorinated alkyl sulfonate, for example potassium perfluorobutane sulfonate (" KPFBS " is also referred to as " Rimar salt ") and potassium diphenylsulfone sulfonate (" KSS ").U.S. Patent No. 3,775,367 have described the application of fluorinated alkyl sulfonate in polycarbonate resin.Yet the polycarbonate resin that these materials are filled with glass separately uses and the benefit of acquisition is limited, and in fact generally includes other additive.The traditional method that is used to strengthen these type of composition flame retardant propertiess is to add soluble organic halogen addictive.Yet halogenate additive is inapplicable for requiring to meet " ECO-friendly (ECO-friendly) " this composition than new standard.
Summary of the invention
Find surprisingly, in the polycarbonate compositions that glass is filled, add the phosphorated alcohol acid and can improve its flame retardant properties substantially.Thereby, the invention provides a kind of method of making the polycarbonate resin of fire-retardant glass filling, comprise the phosphorated alcohol acid that adds effective flame retardance volume to resin.In the time of suitably, come the melt strength of reinforced polycarbonate and can also further strengthen this performance by adding one or more fire retardants by adding dripping inhibitor.Use this composition results to make material have excellent flame-retardant.
Detailed Description Of The Invention
The invention provides a kind of method of making the polycarbonate resin of fire-retardant glass filling by the phosphorated alcohol acid that adds significant quantity in the polycarbonate resin of filling to glass.On the other hand, the invention provides the poly carbonate resin composition of glass filling with flame retardant resistance.Said composition comprises the phosphorated alcohol acid fire retardant of polycarbonate resin and effective flame retardance volume.Also have on the one hand, the invention provides the polycarbonate compositions of the fireproof glass filling that further contains fire retardant and dripping inhibitor.Again on the other hand, the invention provides the goods that comprise said composition, the wherein said goods initially possibility by Underwriters Laboratory standard (Underwriter Laboratories Standard) UL94 test are 90% bigger, and this standard is introduced as a reference at this.
Polycarbonate resin that this method is used and composition of the present invention can and can be made by any method for any grade.Thereby for example, polycarbonate can make by interfacial or scorification (catalytic transesterification).Structurally, polycarbonate not only can but also can be line style for branching, and can comprise sense substituent.The present invention also comprises Copolycarbonate, and term " polycarbonate " should be interpreted as comprising the blend of multipolymer and itself and other thermoplastics.The technology of making polycarbonate by these methods is known, and for example United States Patent(USP) Nos. 3,030,331,3,169,121,4,130,548,4,286,083,4,552,704,5,210,268 and 5,606, and 007 is described.What often use is the combination of two or more different molecular weight polycarbonate.
Be used for glass fibre of the present invention and be well known to a person skilled in the art and can providing by many manufacturerss widely.For the composition that finally is used for electrical application, the preferred glass fiber that contains lime-aluminium borosilicate glass of no sodium relatively that uses.It is called " E " glass.Yet, also can use other glass composition.All these glass are included in the scope of the invention.These silks make by standard method, for example, and by blowing steam or air, flame blowing and mechanical stretching.These are preferred for plastics enhanced silk and make by mechanical stretching.Filament diameter is preferably about 0.00075 inch of about 0.00012-, but this is unimportant to the present invention.Yet the known less filament diameter of those skilled in the art can also increase the intensity by the plastics of its processing.
The length of glass yarn and no matter they whether boundling become fiber and these fibers whether again boundling become yarn, rope or rove or be made into felt etc., all inessential to the present invention.Yet, in preparation moulding compound of the present invention, use length to be about 1/8 thread glass usually to about 2 inches chopped strand form.On the other hand, in the moulded parts that makes by said composition,, in mixing process, also can take place considerable crackedly, thereby even can use shorter length even glass yarn length is shorter.
The glass fibre that the present invention uses can be handled with chemical coating, and this chemical coating is called " starching " agent.The example of sizing agent that can be used for glass fibre is just like at U.S. Patent number 6,405, described in 759.The example of some sizing agent (for example comprises the film-forming polymer material, the low molecular weight epoxy emulsion), organo silane coupling agent or tackifier, positively charged ion or non-ionic lubricant, processing aid, silane, organo-functional group silane are (for example, 3-glycidoxypropyltrime,hoxysilane, 3-aminopropyltriethoxywerene werene and 3-methacryloxypropyl trimethoxy silane), linking agent (for example, disilane) and antioxidant.
Can also add fire retardant in the composition.The available fire retardant is chloride and bromide not.It generally is included in the alkali and an alkali metal salt of the following compounds that is used as fire retardant in the polycarbonate compositions, and they are: monomer or polymeric aromatic sulfonic acid; Monomer or polymeric aromatic sulfones sulfonic acid; The sulfonic acid of aromatic ketone, heterocycle sulfonic acid; Fluoridize methylsulfonic acid; Fluoridize non-aromatic carboxylic acid; The sulfonic acid of aromatics sulfide; Monomer or polymeric aromatic oxide sulfonic acid; Aliphatics and olefinic sulfonic acid; Replacement or oxyfluoride be not for carbonacid; The monomer of sulfonic acid or polymeric aromatic carboxylic acid and ester; Fluoro cycloaliphatic aromatic sulfonic acid; Monomer or polymeric aramid sulfonic acid; And contain the mixture of at least a above-mentioned alkali or an alkali metal salt.Preferred fire retardant is a fluorinated alkyl sulfonate, for example an alkali metal salt (for example, potassium).Specifically, the non-limiting example of Shi Yi sulfonate is fluorinated alkyl sulfonate basic metal, C
1-C
6Alkylammonium or ammonium salt.Described this salt in above-mentioned U.S. Patent No. 3,775,367, this salt comprises that for example, salt is perfluoro-methyl sodium butane sulfonate, potassium or tetraethyl ammonium for example; Perfluoromethane sodium sulfonate, potassium or tetraethyl ammonium; R 116 sodium sulfonate, potassium or tetraethyl ammonium; Perfluoropropane sodium sulfonate, potassium or tetraethyl ammonium; Perflexane sodium sulfonate, potassium or tetraethyl ammonium; PF 5070 sodium sulfonate, potassium or tetraethyl ammonium; Perfluorooctane sulfonates sodium, potassium or tetraethyl ammonium; Perfluorinated butane sodium sulfonate, potassium or tetraethyl ammonium; And tetradifon-3-sodium sulfonate, potassium or tetraethyl ammonium; And contain the mixture of at least a above-mentioned salt.Preferred especially potassium perfluorobutane sulfonate (KPFBS) and tetradifon-3-potassium sulfonate (KSS).The use that also can combine of these sulfonate with the salt (for example, sodium salt) of toluenesulphonic acids.
In the inventive method and containing in the composition of polycarbonate, the sylvite amount of fluorinated alkyl sulfonate is low to moderate least cost aptly, for example 0.004-0.05 weight %, more preferably 0.008-0.03 weight %.The sodium salt amount of toluenesulphonic acids is suitably 0.001-0.1 weight %, more preferably 0.005-0.05 weight %.The combination of the sodium salt of the potassium metal-salt of the fluorinated alkyl sulfonate of preferred especially at least 0.009 weight % and the toluenesulphonic acids of at least 0.005 weight %, for example sodium salt of the toluenesulphonic acids of the sylvite of the fluorinated alkyl sulfonate of 0.001-0.05% and 0.005-0.2%.
Flame-retarded polycarbonate resin of the present invention can also comprise dripping inhibitor.In present specification and claim, term " dripping inhibitor " refers to a kind of additive, and it can improve the melt strength of polycarbonate, thereby when being heated near fusion, reduces the tendency of resin drippage.The example of suitable dripping inhibitor comprises PTFE-base dripping inhibitor, for example 1/1 dispersion, emulsion-based PTFE and the steam precipitation PTFE of PTFE in the styrene acrylonitrile resin.Amount with effective raising melt strength and minimizing drippage adds dripping inhibitor, for example 0.05-0.5 weight %.Teflon resin is well known in the art.Teflon resin is generally finely divided solid, when it is carried out mechanical shearing, has the ultra-fine fibrillar ability of formation.Tetrafluoroethylene is commercially available, is generally aqeous suspension.In order to reduce dispersiveness, preferably in the resin matrix of for example thermoplastic resin, the teflon resin particle is carried out pre-dispersed, this thermoplastic resin, european patent application No.899 for example, the styrene acrylonitrile of instruction in 303.The teflon resin particulate granularity that is coated is generally about 70 microns of about 35-, about 65 microns of preferably about 40-.The consumption of teflon resin based on the gross weight of polycarbonate, is generally less than about 0.1 weight percentage (weight %), preferably is less than or equal to about 0.075 weight %, and is more preferably less than or equals about 0.05 weight %.Must use fluorinated polyolefin with the amount that can effectively prevent composition drippage between heating period, generally more than or equal to about 0.025 weight %.
The present invention further comprises the phosphorated alcohol acid.More preferably acid comprises one of following: phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, diphosphanetetroic acid, phospho acid, phosphonic acids, metaphosphoric acid, hexa metaphosphoric acid, thiophosphoric acid, hexafluorophosphoric acid, difluorophosphoric acid, fluorine phosphorous acid, difluoro phosphorous acid, fluorine Hypophosporous Acid, 50 or fluorine diphosphanetetroic acid.
Preferred phosphorated alcohol acid:
(1) have the alcohol acid that contains many protons phosphorus of following general formula,
H
mP
tO
n
Wherein m and n be 2 or bigger and t be 1 or bigger; Or
(2) have three esters of the acid that contains many protons phosphorus of following general formula,
(R
1O)(R
2O)(R
3O)H
xP
yO
z-3
Wherein x can for 0 or positive integer and z can be 3 or bigger, y is 1 or bigger; And R
1, R
2, and R
3Be organic group.The effective flame retardance volume of phosphorated alcohol acid is such amount, and the composition that promptly contains this amount is compared with the other same combination that does not contain fire retardant, can increase the flame retardant resistance of the polycarbonate of glass filling.
Though the concrete grammar of unqualified test flame retardant resistance, operable usual way comprise formation by extruding molded batten of polycarbonate and the standard of use Underwriters Laboratory UL94 testing method, this standard is incorporated herein as a reference.By calculate average flame out time (flame outtime) (avFOTsec), the standard deviation (sdFOTsec) of flame out time and total number of drops come data are analyzed, and use statistical method that these data are converted to the specific sample prescription reaches V0 and pass through " pass through " first time of rate (first time pass) probability in 5 battens being carried out conventional UL94 test prediction, or " p (FTP) ".P (FTP) is preferably as far as possible near 1, and for example greater than 0.9, and more preferably greater than 0.95, wherein 1 represents the maximum flame that UL tests.
Can also in the polycarbonate resin of this method and composition of the present invention, add this area other additive commonly used.These additives comprise, but are not limited to, stablizer, releasing agent, photostabilizer, thermo-stabilizer, pigment, dyestuff, and filler.
In an embodiment, the polycarbonate resin that glass of the present invention is filled can contain the fire retardant of the sodium salt of sylvite that comprises fluorinated alkyl sulfonate and the toluenesulphonic acids of choosing wantonly.Even because the flame retardant resistance that the polycarbonate that this glass is filled also can obtain for material sheet, thereby it is particularly suitable for making thin-gage goods, and for example wall thickness is less than 1.5mm, i.e. the goods of 1mm-1.5mm.These goods can be by injection molding, extrude or moulding is carried out in blowing.
In some exemplary composition of the present invention, composition contains less than the fire retardant of 0.7phr with less than the phosphorous acid of 0.00009phr.
With reference to following indefiniteness embodiment, with the present invention is described further.
Embodiment 1
Three different ingredients that use has the polycarbonate of different Rimar salt carrying capacity carry out battery of tests.Data in the table 1 show that Rimar salt carrying capacity should be less than 0.07phr.In the application's scope, " phr " is the abbreviation of " umbers of each hundred parts of resin ".This term is a weight determination, and the umber of wherein getting polycarbonate is expressed as 100 parts, and comes more every kind of other component by this polycarbonate gross weight umber for the basis.For example, if use 100 gram polycarbonate, the other component that 1 gram is blended in wherein is 1phr.The unit of all values in these tables is phr.(unit of resin is %)
Table 1
| Criticize 1 | Criticize 2 | Criticize 3 | |
| High workability PC | 45 | 45 | 45 |
| 100 grades of PC | 55 | 55 | 55 |
| Glass fibre | 10.25 | 10.25 | 10.25 |
| Releasing agent | 0.27 | 0.27 | 0.27 |
| Thermo-stabilizer | 0.06 | 0.06 | 0.06 |
| Dripping inhibitor | 0.15 | 0.15 | 0.15 |
| Rimar | 0.05 | 0.06 | 0.07 |
| p(FTP)@62mils | 0.73 | 0.48 | Drip |
Observation for above-mentioned batch 3 drippage shows that the carrying capacity of Rimar salt in the prescription should be less than 0.07phr.In table 1, high workability PC is meant molecular weight about 21,600-22,200 (use the polycarbonate standards thing, according to the gel permeation chromatography molecular weight) the bisphenol-a polycarbonate homopolymer, 100 grade PC are meant molecular weight about 29,500-30,300 bisphenol-a polycarbonate homopolymer, glass fibre is meant that trade mark is the dried chopped strand fibre-grade 415A (with the nonbonding grade of silane starching) (4mm is long) of Owens Corning CRATEC, releasing agent is four stearic acid season ethanol esters (pentaethyritoltetrastearate), thermo-stabilizer is IRGAPHOS 168 (three (2,4-a two-butyl phenyl) phosphite), and dripping inhibitor is a polytetrafluoroethylene (PTFE), it is a potassium perfluorobutane sulfonate for above-mentioned 1/1 dispersion and the Rimar salt that is prepared into PTFE in the styrene acrylonitrile resin emulsion.
Use statistics " UL instrument " to carry out the combustibility test, wherein in this statistics " UL instrument ", use the UL94 testing scheme that 20 battens (rather than 5 common battens) with specific thicknesses are burnt, and calculate the standard deviation (SD) of average flame out time and this flame out time, be converted into subsequently and estimate for the first time of being write down in these tables, replace UL94 the passing through/fail criteria of simple and less indication in testing with this by the numerical value of the probability of " p[FTP] " value.
Embodiment 2
Use has different two different polycarbonate prescriptions of the polycarbonate of carrying capacity relatively and carries out battery of tests.The results are shown in Table 2.Repeat identical test and the results are summarized in the table 3.These results are inconsistent, thereby are difficult to be reached a conclusion by these experiments.Component utilized identical with described in the embodiment 1.
Table 2
| Criticize 1 | Criticize 2 | |
| High workability PC | 35 | 40 |
| 100 grades of PC | 65 | 60 |
| Glass fibre | 10.25 | 10.25 |
| Releasing agent | 0.27 | 0.27 |
| Thermo-stabilizer | 0.06 | 0.06 |
| Dripping inhibitor | 0.15 | 0.15 |
| Rimar | 0.055 | 0.055 |
| p(FTP)@62mils | 0.79 | 0.94 |
Table 3
| Criticize 1 | Criticize 2 | |
| High workability PC | 35 | 40 |
| 100 grades of PC | 65 | 60 |
| Glass fibre | 10.25 | 10.25 |
| Releasing agent | 0.27 | 0.27 |
| Thermo-stabilizer | 0.06 | 0.06 |
| Dripping inhibitor | 0.15 | 0.15 |
| Rimar | 0.055 | 0.055 |
| p(FTP)@62mils | 0.97 | 0.7 |
Embodiment 3
Some different ingredients that use contains above-mentioned dripping inhibitor and Rimar salt fire retardant carry out battery of tests.The results are shown in Table 4.Except phosphorous acid, component utilized identical with described in the embodiment 1.Being prepared as follows of phosphorous acid solution is with 99 gram deionized water dilutions, 1 gram, the 45 weight % aqueous solution.The gross weight of the phr numerical value of the phosphorous acid of record and diluting soln is corresponding in the table 4.Data presentation in the table 4 adds the flame retardant resistance that a small amount of moisture phosphorous acid that dilutes is improved equally.0.9 above flame retardance performance values is considered to acceptable.
Table 4
| Criticize 1 | Criticize 2 | Criticize 3 | Criticize 4 | Criticize 5 | Criticize 6 | |
| High workability PC | 40 | 40 | 40 | 40 | 40 | 40 |
| 100 grades of PC | 60 | 60 | 60 | 60 | 60 | 60 |
| Glass fibre | 10.25 | 10.25 | 10.25 | 10.25 | 10.25 | 10.25 |
| Releasing agent | 0.27 | 0.27 | 0.27 | 0.27 | 0.27 | 0.27 |
| Thermo-stabilizer | 0.06 | 0.06 | 0.06 | 0.06 | 0.06 | 0.06 |
| Dripping inhibitor | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 |
| Rimar | 0.055 | 0.055 | 0.055 | 0.055 | 0.055 | 0.055 |
| Phosphorous acid | 0.02 | 0.04 | 0.06 | 0.08 | 0.1 | |
| p(FTP)@62mils | 0.88 | 0.96 | 0.93 | 0.96 | 0.92 | 0.98 |
Embodiment 4
Some different ingredients that use contains above-mentioned dripping inhibitor and Rimar salt fire retardant carry out battery of tests, but add second fire retardant (that is toluenesulfonic acid sodium salt).In table 5, " NaTS " is means sodium tosylate.In other cases, component utilized with described in above-mentioned these embodiment and the record identical.Data in the table 5 show that the best carrying capacity of phosphorous acid solution is 0.0963phr, and about carrying capacity more than 0.2 has disadvantageous effect to the combustionproperty of this prescription.
Table 5
| Criticize 1 | Criticize 2 | Criticize 3 | Criticize 4 | Criticize 5 | Criticize 6 | Criticize 7 | |
| High workability PC | 35 | 35 | 35 | 35 | 35 | 35 | 35 |
| 100 grades of PC | 65 | 65 | 65 | 65 | 65 | 65 | 65 |
| Glass fibre | 10.25 | 10.25 | 10.25 | 10.25 | 10.25 | 10.25 | 10.25 |
| Releasing agent | 0.27 | 0.27 | 0.27 | 0.27 | 0.27 | 0.27 | 0.27 |
| Thermo-stabilizer | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
| Dripping inhibitor | 0.16 | 0.16 | 0.16 | 0.16 | 0.16 | 0.16 | 0.16 |
| Rimar | 0.015 | 0.015 | 0.015 | 0.015 | 0.015 | 0.015 | 0.015 |
| NaTS | 0.015 | 0.015 | 0.015 | 0.015 | 0.015 | 0.015 | 0.015 |
| Phosphorous acid | 0.0275 | 0.055 | 0.0963 | 0.1375 | 0.29 | 0.75 | |
| p(FTP)@62mils | 0.477 | 0.902 | 0.953 | 0.992 | 0.962 | 0.387 | 0.277 |
Though with reference to some preferred version the present invention has been carried out very detailed description, other scheme can also have been arranged.Therefore, the design of claims and scope are not limited in the content that preferred version of the present invention comprises.
Claims (17)
1. composition, it comprises:
A) first polycarbonate,
B) glass multifilament,
C) fire retardant,
D) dripping inhibitor and
E) the phosphorated alcohol acid of effective flame retardance volume.
2. the composition of claim 1, it comprises that further molecular weight is different from second polycarbonate of first polycarbonate.
3. the composition of claim 1, wherein fire retardant is a fluorinated alkyl sulfonate.
4. the composition of claim 3, wherein fire retardant has alkali metal cation.
5. the composition of claim 3, wherein fire retardant has Si Wan Ji phosphonium cation.
6. the composition of claim 1, wherein dripping inhibitor is PTFE.
7. the composition of claim 1, wherein the phosphorated dripping inhibitor is selected from phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, diphosphanetetroic acid, phospho acid, phosphonic acids, metaphosphoric acid, hexa metaphosphoric acid, thiophosphoric acid, hexafluorophosphoric acid, difluorophosphoric acid, fluorine phosphorous acid, difluoro phosphorous acid, fluorine Hypophosporous Acid, 50 and fluorine diphosphanetetroic acid.
8. the composition of claim 3, wherein said composition comprises the fire retardant less than 0.07phr.
9. the composition of claim 1, wherein containing the phosphorous alcohol acid is phosphorous acid, and said composition comprises the phosphorous acid less than 0.2phr.
10. the composition of claim 1, wherein fire retardant is a perfluoroalkyl salt, and dripping inhibitor is PTFE and to contain the phosphorous alcohol acid be phosphorous acid, and wherein said composition comprises less than the fire retardant of 0.07phr with less than the phosphorous acid of 0.2phr.
11. goods that comprise the composition of claim 1, wherein said goods meet the V0 grade of Underwriters Laboratory standard UL94.
12. a composition, it is composed of the following components basically:
A) one or more polycarbonate,
B) glass multifilament,
C) fire retardant,
D) dripping inhibitor,
E) the phosphorated alcohol acid of effective flame retardance volume and
F) releasing agent and
G) optional colorant or pigment.
13. an improvement contains the method for flame retardant properties of the composition of polycarbonate and a large amount of glass yarn, described method comprises to what described composition added significant quantity and contains the phosphorous alcohol acid.
14. a composition, it comprises:
A) polycarbonate,
B) the glass multifilament and
C) effective flame retardance volume contains the phosphorous alcohol acid.
15. the composition of claim 14, it further comprises fire retardant.
16. the composition of claim 14, it further comprises dripping inhibitor.
17. the composition of claim 15, it further comprises dripping inhibitor.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US43374002P | 2002-12-16 | 2002-12-16 | |
| US60/433,740 | 2002-12-16 | ||
| US10/632,584 | 2003-08-01 |
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| CN100516125C CN100516125C (en) | 2009-07-22 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101511937B (en) * | 2006-07-12 | 2012-07-18 | 沙伯基础创新塑料知识产权有限公司 | Flame retardant and chemical resistant thermoplastic polycarbonate compositions |
| CN106459571A (en) * | 2014-04-28 | 2017-02-22 | 法雷奥照明公司 | Thermoplastic composition |
| CN108727632A (en) * | 2018-06-28 | 2018-11-02 | 浙江大学 | TPE compounding halogen-free flame-retardant system and its application based on dialkyl dithio hypophosphites |
| CN108794804A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | The halogen-free flame-retardant system and its application of dialkyl dithio hypophosphites and nitrogenous compound collaboration |
| CN108794808A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | The thio hypophosphite fire retardant of dialkyl group list and its application |
| CN110650999A (en) * | 2017-04-25 | 2020-01-03 | 沙特基础工业全球技术公司 | Non-brominated non-chlorine flame retardant glass filled polycarbonate with improved multi axial impact strength |
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| TWI564379B (en) * | 2011-04-29 | 2017-01-01 | 奇美實業股份有限公司 | Fire-retardant composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101511937B (en) * | 2006-07-12 | 2012-07-18 | 沙伯基础创新塑料知识产权有限公司 | Flame retardant and chemical resistant thermoplastic polycarbonate compositions |
| CN106459571A (en) * | 2014-04-28 | 2017-02-22 | 法雷奥照明公司 | Thermoplastic composition |
| CN110650999A (en) * | 2017-04-25 | 2020-01-03 | 沙特基础工业全球技术公司 | Non-brominated non-chlorine flame retardant glass filled polycarbonate with improved multi axial impact strength |
| CN110650999B (en) * | 2017-04-25 | 2021-12-28 | 沙特基础工业全球技术公司 | Non-brominated non-chlorine flame retardant glass filled polycarbonate with improved multi axial impact strength |
| US11505696B2 (en) | 2017-04-25 | 2022-11-22 | Sabic Global Technologies B.V. | Non-bromine, non-chlorine flame retardant, glass filled polycarbonate with improved multi-axial impact strength |
| US11926732B2 (en) | 2017-04-25 | 2024-03-12 | Sabic Global Technologies B.V. | Non-bromine, non-chlorine flame retardant, glass filled polycarbonate with improved multi-axial impact strength |
| CN108727632A (en) * | 2018-06-28 | 2018-11-02 | 浙江大学 | TPE compounding halogen-free flame-retardant system and its application based on dialkyl dithio hypophosphites |
| CN108794804A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | The halogen-free flame-retardant system and its application of dialkyl dithio hypophosphites and nitrogenous compound collaboration |
| CN108794808A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | The thio hypophosphite fire retardant of dialkyl group list and its application |
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