CN115746532A - Laser-engravable halogen-free flame-retardant reinforced polycarbonate material for relay and preparation method thereof - Google Patents
Laser-engravable halogen-free flame-retardant reinforced polycarbonate material for relay and preparation method thereof Download PDFInfo
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- CN115746532A CN115746532A CN202211512419.6A CN202211512419A CN115746532A CN 115746532 A CN115746532 A CN 115746532A CN 202211512419 A CN202211512419 A CN 202211512419A CN 115746532 A CN115746532 A CN 115746532A
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- flame retardant
- polycarbonate
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- halogen
- free
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 92
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 79
- 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 78
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000835 fiber Substances 0.000 claims abstract description 19
- 238000010329 laser etching Methods 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims abstract description 9
- 238000010147 laser engraving Methods 0.000 claims abstract description 8
- 229910052705 radium Inorganic materials 0.000 claims abstract description 7
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 10
- 229920005668 polycarbonate resin Polymers 0.000 claims description 9
- 239000004431 polycarbonate resin Substances 0.000 claims description 9
- 239000012745 toughening agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000007974 melamines Chemical class 0.000 claims description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims 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 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- HWXBQOWZWWYBLY-UHFFFAOYSA-N C1(=CC=CC=C1)S(=O)(=O)OS(=O)(=O)C=1C=CC=CC1.[K] Chemical compound C1(=CC=CC=C1)S(=O)(=O)OS(=O)(=O)C=1C=CC=CC1.[K] HWXBQOWZWWYBLY-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- HRKAMJBPFPHCSD-UHFFFAOYSA-N Tri-isobutylphosphate Chemical compound CC(C)COP(=O)(OCC(C)C)OCC(C)C HRKAMJBPFPHCSD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 2
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 claims 1
- FEEPBTVZSYQUDP-UHFFFAOYSA-N heptatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O FEEPBTVZSYQUDP-UHFFFAOYSA-N 0.000 claims 1
- FHSJASSJVNBPOX-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O FHSJASSJVNBPOX-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 239000003990 capacitor Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 239000004033 plastic Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 101000760663 Hololena curta Mu-agatoxin-Hc1a Proteins 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
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- 230000005518 electrochemistry Effects 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 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
- 239000008188 pellet Substances 0.000 description 1
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- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of high polymer materials, and particularly relates to a radium carving halogen-free flame-retardant reinforced polycarbonate material for a relay and a preparation method thereof. The polycarbonate material comprises medium-viscosity polycarbonate, low-viscosity polycarbonate, alkali-free chopped fibers, flame-retardant master batches, phosphorus-nitrogen flame retardant and laser etching auxiliary agents, and the mass ratio of the polycarbonate material to the alkali-free chopped fibers is (34-66): (10-20): (10-20): (8-10): (3-8): (1-3), wherein the melt flow rate of the medium-viscosity polycarbonate is 8-10 g/10min (300 ℃,1.2 kg); the melt flow rate of the low-viscosity polycarbonate is 20 to 22g/10min (300 ℃,1.2 kg). The laser-engravable halogen-free flame-retardant reinforced polycarbonate material provided by the invention can greatly meet the laser engraving (black and white) requirements, has higher GWIT and CTI values, has a better flame-retardant effect, and can be used for products in the fields of electronic appliances such as low-voltage electronic capacitor shells, load break switches, molded case circuit breakers and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a laser-engravable halogen-free flame-retardant reinforced polycarbonate material for a relay and a preparation method thereof.
Background
Polycarbonate is a polymer produced and applied in large scale, and is not only used in the fields of automobiles, electronics and electrics, building materials, rail transit, household appliances and the like due to the special mechanical properties, high transparency, strong tinting strength, good heat resistance, excellent electrical properties and the like. In the application aspect of the low-voltage electrical appliance industry, the PC can not completely replace the traditional PBT and PA, but the PC can achieve better performance balance in the halogen-free aspect and has higher cost performance. The traditional halogen flame-retardant material can achieve the flame-retardant effect, but the halogen-containing smoke released during combustion causes great harm to human bodies. And the PC can improve the flame retardant property, CTI, GWIT and other properties of the material through flame retardant, reinforcing, toughening and other modification technologies, and can be widely applied to the low-voltage electronic and electrical appliance industry.
The marks for identification, such as trademarks, bar codes and numbers, on the traditional relay housing products are usually generated by external processing methods, such as screen printing and label sticking, or by directly machining the surface of a plastic product, such as stamping, engraving and punching, to form marks. However, the identification on the merchandise becomes blurred and incomplete due to mechanical damage, friction and the like during the storage and transportation of the merchandise, so that the identification is not clear; even after the product is used for a period of time, the marks on the surface of the product can be worn away or faded away, which makes the identification difficult.
Laser engraving is a technique that uses the thermal effect of a laser to ablate the surface material of an object leaving a permanent mark. Compared with the traditional marking methods such as electrochemistry, machinery and the like, the method has the advantages of no pollution, high speed, high quality, high flexibility, no contact with a working surface and the like. However, laser engraving has relatively higher requirements for the marking material itself.
For common polycarbonate materials, the absorption of incident laser is not strong, so that the plastic is not easy to generate marks under the irradiation of laser energy, but after the energy is increased, the phenomena of insufficient mark contrast or yellow mark color and the like obtained on the surface of the material cannot meet the requirement of clear marks.
Disclosure of Invention
In order to solve the problem that the existing polycarbonate materials mentioned in the background art do not absorb incident laser light strongly and are not easy to generate marks. The invention provides a laser-engravable halogen-free flame-retardant reinforced polycarbonate material for a relay, which comprises the following components: medium-viscosity polycarbonate, low-viscosity polycarbonate, alkali-free chopped fibers, flame-retardant master batches, phosphorus-nitrogen flame retardants and laser etching aids;
the ratio of the medium-viscosity polycarbonate to the low-viscosity polycarbonate to the alkali-free chopped fiber to the flame-retardant master batch to the phosphorus-nitrogen flame retardant to the laser etching auxiliary agent is (34-66): (10-20): (10-20): (8-10): (3-8): (1-3) of the total weight of the composition,
wherein the melt flow rate of the medium viscosity polycarbonate is 8-10 g/10min (300 ℃,1.2 kg); the low-viscosity polycarbonate has a melt flow rate of 20 to 22g/10min (300 ℃,1.2 kg).
In one embodiment, the polycarbonate resin is at least one of an aliphatic polycarbonate resin, an aromatic polycarbonate resin, and an aliphatic-aromatic polycarbonate resin.
In one embodiment, the alkali-free chopped fibers are PC specialty glass fibers, preferably boulders 510, 510H.
In one embodiment, the flame-retardant master batch is a master batch prepared by mixing one or more of potassium perfluorobutylsulfonate, potassium 3-benzenesulfonyl benzenesulfonate and polytetrafluoroethylene in any proportion.
In one embodiment, the phosphorus-nitrogen flame retardant comprises a phosphorus flame retardant and a nitrogen flame retardant, wherein the phosphorus flame retardant is at least one of triphenyl phosphate, triisobutyl phosphate, tricresyl phosphate, tolylene diphenyl phosphate and condensed aryl phosphate, and the nitrogen flame retardant is at least one of melamine, melamine salt and ammonium polyphosphate.
In one embodiment, the phosphorus-nitrogen flame retardant is composed of a phosphorus flame retardant and a nitrogen flame retardant in a mass ratio of 1.
The phosphorus-nitrogen flame retardant is compounded with the phosphorus flame retardant, and the non-combustible gas generated by the nitrogen flame retardant and a carbide layer generated by the phosphorus flame retardant are utilized to generate a synergistic effect, so that the efficient halogen-free flame retardance of the composite material is realized, and the electrical performance of the polycarbonate is not influenced.
The laser etching auxiliary agent is at least one of antimony trioxide, bismuth oxide, silicon dioxide, carrier-free carbon black master batch and organic black master batch.
In one embodiment, the toner further comprises a toughening agent, an antioxidant, a lubricant and a toner.
Further, the flame-retardant polyester comprises, by weight, 34-66 parts of medium-viscosity polycarbonate, 10-20 parts of low-viscosity polycarbonate, 10-20 parts of alkali-free chopped fibers, 8-10 parts of flame-retardant master batches, 3-8 parts of phosphorus-nitrogen flame retardants, 1-3 parts of laser engraving aids, 1-3 parts of flexibilizers, 0.2-0.5 part of antioxidants, 0.2-0.5 part of lubricants and 1 part of toner.
In one embodiment, the toughening agent is at least one of MBS, GMA, ACR.
In one embodiment, the antioxidant is at least one of triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, and dioctadecyl alcohol pentaerythritol diphosphite.
In one embodiment, the lubricant is at least one of paraffin, silane polymer, fatty acid salt, fatty acid amide, methylene bis stearamide, N-ethylene bis stearamide.
In one embodiment, the toner is composed of 39% organic black BK, 20% iron red, and 22% titanium blue.
The invention also provides a preparation method of the radium engravable halogen-free flame retardant reinforced polycarbonate material for the relay, which comprises the steps of adding all the other raw materials except the alkali-free chopped fibers into a high-speed stirrer, fully and uniformly mixing, feeding the materials into a double-screw extruder through a metering and feeding device after complete mixing, adding the alkali-free chopped fibers from a lateral feed according to a proportion, wherein the temperature of each zone is 220-250 ℃, fully fusing the materials under the shearing, mixing and conveying of a screw, and finally preparing a finished product of granules after extrusion, bracing and cooling to obtain the radium engravable halogen-free flame retardant reinforced polycarbonate material for the relay.
Compared with the prior art, the laser-engravable halogen-free flame-retardant reinforced polycarbonate material provided by the invention can greatly meet the laser engraving (black and white) requirements, can form white marks with obvious contrast on the surface of dark plastic, can not generate adverse phenomena such as plastic degradation damage by heating, mark blurring, marked character yellowing and the like, and simultaneously can have higher GWI T and CT I values, has better flame-retardant effect and excellent comprehensive performance, and can be widely applied to products in the field of electronic appliances such as low-voltage electronic capacitor shells, load circuit breakers, molded case breakers and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a radium carving halogen-free flame-retardant reinforced polycarbonate material for a relay, which comprises the following steps:
(1) And (3) drying the main material components such as the medium-viscosity polycarbonate, the low-viscosity polycarbonate, the flame-retardant master batch and the like for 2-3 h at the temperature of 120 ℃.
(2) Weighing medium-viscosity polycarbonate, low-viscosity polycarbonate, flame-retardant master batches, phosphorus-nitrogen flame retardants, toughening agents, antioxidants, lubricants and laser etching aids according to a certain weight, and putting the materials into a high-speed stirrer to be fully and uniformly mixed to obtain a mixture M;
(3) Feeding the mixture M into a double-screw extruder through a metering feeding device, feeding alkali-free chopped fibers from the side through the metering feeding device, fully fusing the materials in the double-screw extruder under the shearing, mixing and conveying of screws, and preparing the radium carving halogen-free flame retardant reinforced polycarbonate material for the relay through melting, extruding, bracing and granulating;
wherein the melt extrusion temperature is 220-250 ℃, the length-diameter ratio of a screw of the double-screw extruder is (40-44) to 1, and the rotating speed of the screw is (300-350) rpm.
The invention also provides the following examples and comparative examples:
the formulations (unit: parts by weight) of examples and comparative examples provided by the present invention are shown in tables 1 and 2 below:
TABLE 1
| Components | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Medium viscosity polycarbonates | 53.3 | 52.3 | 51.3 | 57.3 | 43.3 |
| Low viscosity polycarbonates | 15 | 15 | 15 | 15 | 15 |
| Alkali-free chopped fiber | 15 | 15 | 15 | 10 | 20 |
| Flame-retardant master batch | 8 | 8 | 8 | 8 | 8 |
| Flame retardant | 4 | 4 | 4 | 4 | 8 |
| Laser etching auxiliary agent | 1 | 2 | 3 | 2 | 2 |
| Toughening agent | 2 | 2 | 2 | 2 | 2 |
| Antioxidant agent | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Lubricant agent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Toner powder | 1 | 1 | 1 | 1 | 1 |
TABLE 2
| Components | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Medium viscosity polycarbonate | 67.3 | 0 | 52.3 | 52.3 | 52.3 | 54.3 |
| Low viscosity polycarbonates | 0 | 67.3 | 15 | 15 | 15 | 15 |
| Alkali-free chopped fiber | 15 | 15 | 15 | 15 | 15 | 15 |
| Flame-retardant master batch | 8 | 8 | 8 | 8 | 8 | 8 |
| Flame retardant | 4 | 4 | 4 | 4 | 4 | 4 |
| Laser etching auxiliary agent | 2 | 2 | 2 | 2 | 2 | 0 |
| Toughening agent | 2 | 2 | 2 | 2 | 2 | 2 |
| Antioxidant agent | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Lubricant agent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Toner powder | 1 | 1 | 1 | 1 | 1 | 1 |
Except for specific descriptions, the types of the raw material components in the examples and the comparative examples in the table 1 are selected consistently, and the components are as follows:
the medium-low viscosity polycarbonate and the medium-viscosity polycarbonate are aromatic polycarbonate resins, the melt flow rate of the low-viscosity polycarbonate is 22g/10min (300 ℃,1.2 kg), and the melt flow rate of the medium-viscosity polycarbonate is 8g/10 min (300 ℃,1.2 kg);
the alkali-free chopped fiber is giant rock 510H;
the flame-retardant master batch is prepared by mixing, melting, extruding and granulating a flame retardant potassium perfluorobutyl sulfonate and medium-viscosity polycarbonate (melt index is 8g/10 min (300 ℃,1.2 kg)) in a double-screw extruder according to a mass ratio of 1;
the phosphorus-nitrogen flame retardant of the embodiment is specifically prepared by blending triphenyl phosphate and melamine salt according to a ratio of 1;
the laser etching auxiliary agent is commercially available laser etching powder HZ-895;
the toughening agent is MBS;
the antioxidant is prepared by mixing antioxidant 168 (tris (2, 4-di-tert-butylphenyl) phosphite) and antioxidant 1076 (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate) according to a mass ratio of 1;
the lubricant is PETS (pentaerythritol stearate);
the toner consisted of 39% organic black BK, 20% iron red and 22% titanium blue;
the flame retardant of comparative example 3 is a phosphorus flame retardant, specifically triphenyl phosphate;
the flame retardant of comparative example 4 is a nitrogen-based flame retardant, specifically melamine salt;
the flame retardant of comparative example 5 was brominated PC.
The polycarbonate materials prepared in the examples were tested for the relevant performance indexes under the same test conditions, and the test results are shown in tables 3 and 4 below:
TABLE 3
TABLE 4
Note:
melt means, i.e., the test standard for melt flow rate is GBT3682-2000 (equivalent I SO1133: 1997) under test conditions of 300 ℃ and 1.2kg load; the test standard of the tensile strength is I S0527-2, the size of a sample is 1A type (gauge length is 115mm, and the parallel part is 10mm multiplied by 4 mm), and the tensile speed is 50mm/mi n; the test standard of the bending strength and the bending modulus is I SO178, the size of a sample is 80mm multiplied by 10mm multiplied by 4mm, and the bending speed is 2 mm/min;
the test standard of the impact strength of the simply supported beam is I SO179-1, and the size of a sample is 80mm multiplied by 10mm multiplied by 4mm (if a gap exists, the gap is kept to be 8mm in width);
the test standard of the combustion performance of the plastic is UL94, wherein the thickness d of the test sample is 1.0mm;
the flammability index GWFI test standard is IEC60695, 960 ℃/1mm;
compared with the comparative tracking index CTI test standard GB/T4207-2012;
testing the load thermal deformation temperature according to an IS 0/2A method;
hot ball pressure was tested according to standard ASTM D1895-96;
the laser etching effect is evaluated by the same laser etching process of an injection molding color plate on an infrared marking machine, wherein X represents that the laser etching cannot be carried out, O represents that the laser etching can be carried out, and the more the number of the O, the better the laser etching effect.
The molded appearance was measured by injection molding the polycarbonate pellets obtained to form a flat sheet of 100mm x 1.0mm, and visually observing the surface of the sample for fiber floating and integrity.
From the test results of table 2, it can be derived:
the test results of the embodiments 1 to 5 show that the laser-engravable halogen-free flame-retardant reinforced polycarbonate material provided by the invention can greatly meet the laser-engraving (black and white engraving) requirement, can form a white mark with an obvious contrast on the surface of dark plastic, and can not generate the adverse phenomena of thermal degradation damage of the plastic, fuzzy mark, yellowing of marked characters and the like.
Compared with the example, the difference of the comparative example 1 is that low-viscosity polycarbonate is not added, and tests show that the low-viscosity polycarbonate is not added, the molding fluidity is limited, the molding complex structure is easy to be starved, and light and micro floating fibers are easy to appear; comparative example 2 differs from the examples in that no medium viscosity polycarbonate is added, and tests show that the fluidity is better, but the mechanical properties are poorer; therefore, the proportion of the low-viscosity polycarbonate to the medium-viscosity polycarbonate in the whole system is particularly important, and the mechanical property of the finished product material can be ensured on the premise of good molding fluidity.
Compared with the embodiment, the comparative example 3 is different in that the phosphorus flame retardant is adopted to replace the phosphorus-nitrogen flame retardant, and the test result shows that the electrical performance is better, but the thermal performance is slightly insufficient; compared with the embodiment, the comparative example 4 is different from the embodiment in that a nitrogen flame retardant is adopted to replace a phosphorus-nitrogen flame retardant, and tests show that the vertical flame retardant effect can only reach V1, so that the nitrogen flame retardant and the phosphorus flame retardant in the phosphorus-nitrogen flame retardant provided by the invention generate synergistic interaction, and the two are not enough.
Compared with the embodiment, the difference of the comparative example 5 is only that brominated PC is used for replacing the phosphorus-nitrogen flame retardant, and tests show that the electrical property CT I effect is obviously not as expected, and CT I can only reach 175V, which shows that compared with the conventional flame retardant, the phosphorus-nitrogen flame retardant provided by the invention can not only improve the flame retardance of materials, but also ensure that the electrical property of polycarbonate is not affected, and meets the requirements of related electronic and electric products.
Compared with the embodiment, the difference of the comparative example 6 is that no laser etching auxiliary agent is added, and the test result shows that the laser etching effect is poor and traces can hardly be formed without adding the laser etching auxiliary agent.
In conclusion, the invention adopts the medium-viscosity polycarbonate and the low-viscosity polycarbonate with specific proportions as the matrix resin, and the phosphorus-nitrogen flame retardant compounded by the phosphorus flame retardant and the nitrogen flame retardant not only ensures the good flow property, mechanical property and flame retardant property of the finished polycarbonate material, but also does not influence the electrical property of the material, so that the polycarbonate material can be widely used for products in the fields of electronic appliances such as low-voltage electronic capacitor shells, load break switches, molded case circuit breakers and the like.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The laser-engravable halogen-free flame-retardant reinforced polycarbonate material for the relay is characterized by comprising the following components: medium-viscosity polycarbonate, low-viscosity polycarbonate, alkali-free chopped fibers, flame-retardant master batches, phosphorus-nitrogen flame retardants and laser etching aids;
the ratio of the medium-viscosity polycarbonate to the low-viscosity polycarbonate to the alkali-free chopped fiber to the flame-retardant master batch to the phosphorus-nitrogen flame retardant to the laser etching auxiliary agent is (34-66): (10-20): (10-20): (8-10): (3-8): (1-3) of the total weight of the composition,
wherein the melt flow rate of the medium-viscosity polycarbonate is 8-10 g/10min; the melt flow rate of the low-viscosity polycarbonate is 20 to 22g/10min.
2. The relay-use laser-engravable halogen-free flame retardant reinforced polycarbonate material as claimed in claim 1, wherein the polycarbonate resin is at least one of aliphatic polycarbonate resin, aromatic polycarbonate resin and aliphatic-aromatic polycarbonate resin.
3. The relay laser engravable halogen-free flame retardant reinforced polycarbonate material as claimed in claim 1, wherein the flame retardant master batch is a master batch prepared by mixing one or more of potassium perfluorobutylsulfonate, potassium 3-benzenesulfonyl benzenesulfonate and polytetrafluoroethylene in any proportion.
4. The relay laser engravable halogen-free flame retardant reinforced polycarbonate material as claimed in claim 1, wherein the phosphorus-nitrogen flame retardant comprises phosphorus flame retardant and nitrogen flame retardant, the phosphorus flame retardant is at least one of triphenyl phosphate, triisobutyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate and condensed aryl phosphate, and the nitrogen flame retardant is at least one of melamine, melamine salt and ammonium polyphosphate.
5. The relay-use laser-engravable halogen-free flame-retardant reinforced polycarbonate material as claimed in claim 1, wherein the laser-engraving auxiliary agent is at least one of antimony trioxide, bismuth oxide, silicon dioxide, carrier-free carbon black master batch and organic black master batch.
6. The relay laser engravable halogen-free flame retardant reinforced polycarbonate material as claimed in claim 1, further comprising a toughening agent, an antioxidant, a lubricant and a toner.
7. The relay laser engravable halogen-free flame retardant reinforced polycarbonate material as claimed in claim 6, which comprises the following components, by weight, 34-66 parts of medium viscosity polycarbonate, 10-20 parts of low viscosity polycarbonate, 10-20 parts of alkali-free chopped fiber, 8-10 parts of flame retardant master batch, 3-8 parts of phosphorus-nitrogen flame retardant, 1-3 parts of laser engraving aid, 1-3 parts of toughening agent, 0.2-0.5 part of antioxidant, 0.2-0.5 part of lubricant and 1 part of toner.
8. The relay of claim 7, wherein the toughening agent is at least one of MBS, GMA and ACR.
9. The laser engravable halogen free flame retardant reinforced polycarbonate material for the relay according to claim 6, wherein the antioxidant is at least one of triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, dioctadecyl alcohol pentaerythrityl diphosphite;
the lubricant is at least one of paraffin, silane polymer, fatty acid salt, fatty acid amide, methylene bis-stearic acid amide and N, N-ethylene bis-stearic acid amide;
the toner is organic black BK 39%, iron oxide red 20%, and titanium blue 22%.
10. The preparation method of the radium engravable halogen-free flame retardant reinforced polycarbonate material for the relay according to claims 1-9 is characterized by comprising the following steps:
adding all the other raw materials except the alkali-free chopped fibers into a high-speed stirrer, fully and uniformly mixing, feeding the materials into a double-screw extruder through a metering and feeding device after complete mixing, then adding the alkali-free chopped fibers from a lateral feeding according to a proportion, wherein the temperature of each zone is 220-250 ℃, fully fusing the materials under the shearing, mixing and conveying of screws, and finally preparing into a finished product of granules after extrusion, bracing and cooling to obtain the radium carving halogen-free flame-retardant reinforced polycarbonate material for the relay.
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