CN103059785B - Heat resistant type transparent polyolefin hot melt adhesive and preparing method thereof - Google Patents
Heat resistant type transparent polyolefin hot melt adhesive and preparing method thereof Download PDFInfo
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- CN103059785B CN103059785B CN201210569139.9A CN201210569139A CN103059785B CN 103059785 B CN103059785 B CN 103059785B CN 201210569139 A CN201210569139 A CN 201210569139A CN 103059785 B CN103059785 B CN 103059785B
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- melt adhesive
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 38
- 239000004831 Hot glue Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- -1 ethylene-propylene-1-butene Chemical class 0.000 claims abstract description 21
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 150000003254 radicals Chemical class 0.000 claims description 13
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 5
- 229920000034 Plastomer Polymers 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004902 Softening Agent Substances 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 239000004970 Chain extender Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 claims description 2
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 claims description 2
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 claims description 2
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 claims description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical group CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical group C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 2
- WUMMIJWEUDHZCL-UHFFFAOYSA-N 3-prop-2-enyloxolane-2,5-dione Chemical group C=CCC1CC(=O)OC1=O WUMMIJWEUDHZCL-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical group CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical group CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical group OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 13
- 230000001070 adhesive effect Effects 0.000 abstract description 12
- 238000010292 electrical insulation Methods 0.000 abstract description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 5
- 239000005977 Ethylene Substances 0.000 abstract description 2
- 238000007493 shaping process Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 229920001519 homopolymer Polymers 0.000 abstract 1
- 239000000155 melt Substances 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 14
- 229920006124 polyolefin elastomer Polymers 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 239000012943 hotmelt Substances 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000002313 adhesive film Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 150000008301 phosphite esters Chemical class 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000001336 alkenes Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- RYAIMSPHUVXLQI-UHFFFAOYSA-N 4-(aminomethyl)-2-(benzotriazol-2-yl)phenol Chemical compound NCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 RYAIMSPHUVXLQI-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- LJXTYJXBORAIHX-UHFFFAOYSA-N diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1 LJXTYJXBORAIHX-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002365 multiple layer Substances 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 229950002083 octabenzone Drugs 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000007704 transition Effects 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
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses heat resistant type transparent polyolefin hot melt adhesive and a preparing method thereof. The Heat resistant type transparent polyolefin hot melt adhesive comprises 1) resin, 2) radical initiator, and 3) grafting monomer by weight. The resin includes by weight 70-99% of ethylene-1-octylenecopolymer, 0-5 % of ethylene homopolymer and 1-30 % of ethylene-propylene-1-butene amorphous copolymer. The dosage of the radical initiator covers 0.01-10% of the total mass of the resin. And the grafting monomer covers 0.1-10% of the total mass of the resin. After the components are premixed evenly, a melt grafting reaction is carried out at the temperature of 160-200 DEG C with a double-screw extruder. Then the granulous, sheet and membranaceous hot melt adhesive is manufactured by cooling through the device, pelleting through a pelletizer, shaping into a granulous shape through a vulcanization mechanism. The hot melt adhesive not only has excellent electrical insulation property, optical property, heat resistance property and adhesive property, but also maintains the physical property, chemical stability and good machinability of the polyolefin materials.
Description
Technical field
The present invention relates to hot melt adhesive material field, be specifically related to a kind of heat resistant type transparency polyolefin hot melt adhesive and preparation method thereof.
Background technology
Polyolefine material is based on polyethylene (PE), polypropylene (PP), it is the maximum kind of commodity polymer material, it has excellent physicals, chemical stability, good processibility, can recycle, and there is excellent electrical insulation capability, be widely used in the fields such as packaging industry, automotive industry, electronic industry, along with the development of science and technology, the structurizing of product, functionalization more show important, simple single layer structure can not meet service requirements, needs multilayer material or the bonding of multiple structure unit to meet performance requriements.For electronics industry, glue often bonds conductive component and non conductive component or another one conductive component, this just has high requirements to the electrical insulation capability of glue, polarity hot-fusible high-molecular glue has very high adhesive property, but there is hidden danger in its electrical insulation capability, in electron device, use this hot melt adhesive, probably occur the phenomenon that short circuit and energy waste run off, therefore this field more needs the polyolefin hot-melt of the non-polar conformations that electrical insulating property is higher.Meanwhile, due to polyolefinic non-polar conformations, its water vapor barrier property, weather-proof and ageing-resistant performance is all more excellent, under being more suitable for the physical environment such as outdoor, high humidity.
At present, polyolefin hot-melt is bonding to realize mainly through grafting of polar monomers, it can be multiple polyolefinic mixture, if application scenario requires that polyolefin hot-melt has certain thermotolerance, then multiselect PE, PP is main as matrix resin, because PE, PP have high crystalline, light is different from non-crystalline region in the specific refractory power of crystalline region, and resin is creamy white, translucent even not transparent, the transmittance of the most transparent PE raw material is only 65%, and therefore this hot melt adhesive does not have good optical property, if application scenario requires that polyolefin hot-melt has certain light transmission, the polyolefin elastomer (POE) that then multiselect transmittance is higher, in this resin, flexible octene segment instead of part ethene segment, overall degree of crystallinity reduces, improve the adhesive property of composition to a certain extent, as applicant discloses a kind of novel polyolefin packaging glue film composite and application thereof in patent application CN201110449535.3 before, said composition specifically comprises ethylene-octene copolymer, polyethylene, ethylene methyl methacrylate multipolymer, and linking agent, the composition of oxidation inhibitor and UV stabilizer composition.But the fusing point of said composition is low, generally lower than 60 DEG C, poor heat resistance, because which limit its range of application.
Summary of the invention
In view of the defect of prior art, the object of the present invention is to provide a kind of heat resistant type transparency polyolefin hot melt adhesive, it is made not only to have excellent electrical insulation capability and optical property, and good thermotolerance and adhesive property, and the physicals of polyolefine material excellence, chemical stability and good processibility can also be kept.
Another object of the present invention is to the preparation method that a kind of heat resistant type transparency polyolefin hot melt adhesive is provided.
The technical solution adopted in the present invention is as follows for achieving the above object:
A kind of heat resistant type transparency polyolefin hot melt adhesive, it comprises following component by weight percentage:
A) resin
Ethylene-l-octane copolymer 70-99%
Alathon 0-5%
Ethylene-propylene-1-butylene amorphous copolymer 1-30%;
B) radical initiator, its consumption accounts for the 0.01-0.7% of resin total mass;
C) grafted monomer, accounts for the 0.1-10% of total resin weight.
Grafted monomer described in the present invention is the compound containing alkene functional group or epoxy-functional, the polar monomer that resin macromole gets on can be grafted to by addition or ring-opening reaction, preferably, described grafted monomer is γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidoxypropyltrietandysilane andysilane, γ-(methacryloxy) propyl trimethoxy silicane, γ-Mercaptopropyltriethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl-acetic ester, tertiary ethylene carbonate, propionate, vinyl butyrate, maleat, maleic anhydride, itaconic anhydride, citraconic anhydride, allyl succinic anhydride, hexamethylene-4-alkene-1,2-dicarboxylic anhydride, 4-methylenecyclohex-4-alkene-1,2-dicarboxylic anhydride, dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboxylic anhydride, x-methyl bicycle [2.2.1]-5-in heptan alkene-2,3-dicarboxylic anhydride, glycidyl allyl ether, vinyl glycidyl ether, toxilic acid glycidyl ester, glycidyl itoconate, glycidyl acrylate, glycidyl methacrylate, 2-tetrahydrobenzene-1-base glycidyl ether, tetrahydrobenzene-4,5-diglycidyl carboxylicesters, tetrahydrobenzene-4-glycidyl carboxylicesters, 5-norbornylene-2-methyl-2-glycidyl carboxylicesters, one or more mixing in interior-cis-bicyclo [2.2.1]-5-in heptan alkene-2,3-diglycidyl dicarboxylic ester.The object of grafted monomer and effect are by being grafted to by polyfunctional compound on matrix resin to improve the cohesive strength of matrix resin to different substrate materials.
In order to ensure that this hot melt adhesive has excellent transmittance, matrix resin is based on ethene/1-octene copolymer (POE), and in preferred embodiments of the present invention, in described ethene/1-octene copolymer, the molar content of octene is 20-50%, fusing point is 40-80 DEG C, and weight-average molecular weight is 7000-9000.Can not only ensure under this parameter that the transmittance of POE can also improve the mobility of composition, is beneficial to processing.
In order to improve the thermotolerance of hot melt adhesive on the basis of matrix resin, in preferred scheme, described Alathon (PE) density is 0.90-0.95g/cm
3, fusing point is 80-150 DEG C.Because it belongs to high crystalline material, addition too much can cause the decline of hot melt adhesive transmittance, and therefore its consumption must control 5% and following; If but the consumption of Alathon is too low or do not add Alathon, the thermotolerance of polymkeric substance can be caused again not reach the requirement of application.In order to balance thermotolerance and the light transmission of PE-POE binary system, applicant finds ethylene-propylene-this terpolymer of 1-butylene amorphous copolymer, because the crystallization tendency of propylene is higher than ethene, therefore the polypropylene segments in this polymkeric substance more easily forms the crystallite district of some amount, physical support point plays at polymeric inner in this crystallite district, polymkeric substance is made to occur a high-temperature fusion peak near 110 DEG C, thus the thermotolerance of polymkeric substance can be improved, simultaneously due to region, crystalline region and ratio little, make this polymkeric substance have high transmittance.Therefore, add ethylene-propylene-1-butylene amorphous copolymer in the present invention with Substitute For Partial Alathon, thermotolerance and the light transmission of PE-POE binary system can be balanced, make its two kinds of performances all reach optimum.But because the molecular weight of this polymkeric substance is not high, do not have enough intensity, therefore unaffected in order to ensure the mechanical property of hot melt adhesive, its consumption controls between 1-30%.In preferred embodiments of the present invention, the density of described ethylene-propylene-1-butylene amorphous copolymer is 0.85-0.91g/cm
3, ring and ball softening point is 80-140 DEG C.
In order to balance thermotolerance and the light transmission of this polyolefin hot-melt further, other polyolefin plastomers (POP) parts that the present invention can add fusing point high compared with POE replace POE, POE with POP synthesize time due to monomer content different, there is similar structures, but the thermotolerance of POP is better, therefore under the prerequisite of transmittance not reducing mixture, its thermotolerance can be improved further adding of POP.Because POP resin is not easy grafting, therefore it can not replace POE use completely.The weight percentage of the polyolefin plastomers of adding in preferred the present invention is 5-20%.
In order to make polyolefin resin have cohesiveness, cause resin macromolecular radical grafting of polar monomers group, radical initiator selected by initiator of the present invention.Preferably, the radical initiator adopted in the present invention is 3, two (t-amyl peroxy) ethyl butyrate, 4 of 3-, two (t-butyl peroxy) n-butyl pentanoate, 1 of 4-, two (t-butyl peroxy)-3 of 1-, 5,5-trimethyl-cyclohexane, 2,5,-dimethyl-2,5-is two-and (t-butyl peroxy)-3-hexin, di-t-butyl peroxide, di t-amyl peroxide, t-butylcumylperoxide, two-(tert-butylperoxyiso-propyl) benzene, 2,5-dimethyl-2,5-are two-(t-butyl peroxy) hexane, one or more mixing in dicumyl peroxide.
In preferred scheme, heat resistant type transparency polyolefin hot melt adhesive of the present invention also comprise in free radical activator, chainextender, fire retardant, uv-absorbing agent, photostabilizer, oxidation inhibitor, softening agent, tinting material or white dyes one or more.Wherein, free radical activator can play the effect of Nitroxyl stable radical, extend radical life, reduce the crosslinking reaction degree occurred because coupling stops between macromolecular radical and the DeR degree occurred due to β fracture, improve grafting efficiency.This free radical activator is can roll into a ball containing alkene or the compound of active H, be preferably one of following or wherein two or more mixtures: triallyl isocyanate, triallyl cyanate, Ethylene glycol dimethacrylate, a phenyl-bismaleimide, Viscoat 295, trimethylolpropane trimethacrylate, phthalic acid diisopropyl alkene ester, 1,2-polyhutadiene, ethidine polybutene.In order to extend its work-ing life further, uv-absorbing agent and photostabilizer can be added.Described uv-absorbing agent is selected from benzophenone and benzotriazole category, is preferably one of following or wherein two or more mixtures: the tertiary octyl phenyl of 2-(2'-hydroxyl-5'-) benzotriazole, 2-hydroxyl-4 (2'-hydroxyl-3'-acryloxy propoxy-) benzophenone, Octabenzone, 2-(2'-hydroxyl-5'-aminomethyl phenyl) benzotriazole, N-(2-ethylphenyl)-N'-(2-ethoxyl phenenyl) oxalic acid diamide, 2-(the tertiary octyl phenyl of 2'-hydroxyl-5'-) benzotriazole.Described photostabilizer is selected from hindered amines, is preferably one of following or wherein two or more mixtures: 2,2,6,6-tetramethyl--4-pyridine alcohol fatty acid ester, two (2,2,6,6-tetramethyl--4-piperidyl) sebate, succinic acid and 4-hydroxyl-2,2,6, polymkeric substance, the 4-benzoyloxy-2 of 6-tetramethyl--1-piperidine ethanol, 2,6,6-tetramethyl piperidine.In order to prevent the transition thermooxidative degradation jaundice of composition in blending extrusion process, the present invention can add oxidation inhibitor, and described oxidation inhibitor is selected from Hinered phenols antioxidant, suffocated amine antioxidant, phosphite ester kind antioxidant and thioether kind antioxidant; Preferred Hinered phenols antioxidant and phosphite ester kind antioxidant are also used.The present invention can also add softening agent to improve rheological performance, enhances productivity, and preferred described softening agent is selected from paraffinic mineral oil and aromatic mineral oil, preferred paraffinic mineral oil; They can also improve the wetting property of composition to material to be bonded, improve adhesive property further.Heat resistant type transparency polyolefin hot melt adhesive of the present invention also can add chainextender, fire retardant, tinting material or white dyes to change physics or the mechanical property of hot melt adhesive.
Monomeric grafting processes of the present invention can use method known to those skilled in the art to carry out.Such as solution grafting or melt grafting etc.
A preparation method for heat resistant type transparency polyolefin hot melt adhesive, it comprises the following steps:
The component above-mentioned according to the present invention and consumption by each component premix evenly after; twin screw extruder is used to carry out melting graft reaction at 160-200 DEG C; then cooled by device, through dicing machine granulation, re-use vulcanizer and make granular, sheet and membranaceous hot melt adhesive.
Relative to prior art, beneficial effect of the present invention is: polyolefin hot-melt of the present invention can realize effectively bonding, excellent electrical insulation capability and optical property, there is good thermotolerance and light transmission, and maintain the physicals of polyolefine material excellence, chemical stability and good processibility.The service requirements in the field such as electronic equipment display screen and view port, solar module, mobile phone and tablet personal computer display screen (may use under hot and humid environment) under the electronic display of outdoor application and decoration, high temperature operation can be met.
Below in conjunction with concrete embodiment, the present invention is described in further detail.
Embodiment
It is below the preferred embodiment of the invention.
Raw material of the present invention comprises:
Ethene/1-octene copolymer elastomerics POE that polyolefin elastomer (A) is produced for DOW, commodity are called Engage 8137;
The LLDPE that Alathon (B) is produced for limited-liability company of China Petrochemical Industry, commodity are called DFDA-2001;
Ethylene/propene/1-butylene amorphous copolymer (C) is Evonik production, and commodity are called VESTOPLAST 750;
The polyolefin plastomers POP that polyolefin plastomers (D) is produced for DOW, commodity are called AFFINITY 1140G;
Above-mentioned raw materials is according to following steps machine-shaping: after each component premix is even, uses twin screw extruder to carry out melting graft reaction at 160-200 DEG C, is then cooled by device, through dicing machine granulation, re-use vulcanizer and suppress 0.5 membranaceous hot melt adhesive.Embodiment 1-9 specifically fills a prescription in table 1.
Table 1: resin proportioning (weight percent) in each example
| Composition/% | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| A | 70 | 85 | 98 | 70 | 80 | 75 | 70 | 65 | 70 |
| B | 5 | 3 | 0 | -- | - | - | - | - | - |
| C | 25 | 12 | 2 | 10 | 10 | 15 | 20 | 30 | 25 |
| D | - | - | - | 20 | 10 | 10 | 10 | 10 | 5 |
| Two (t-butyl peroxy) n-butyl pentanoate of 4,4- | 0.2 | 0.3 | 0.1 | 0.1 | 0.3 | 0.05 | 0.3 | 0.2 | 0.2 |
| Maleic anhydride | 3 | 2.5 | 2 | 1 | 1.5 | 2 | - | - | - |
| Vinyltriethoxysilane | - | - | - | - | - | - | 4 | - | - |
| Vinyl-acetic ester | - | - | - | - | - | - | - | 2.5 | - |
| Glycidyl methacrylate | - | - | - | - | - | - | - | - | 8 |
| Triallyl isocyanate | - | - | - | - | - | 1 | 1.5 | 0.8 | 1 |
| Four (3,5-di-t-butyl-4-hydroxyl) phenylpropionic acid pentaerythritol ester (Hinered phenols antioxidant) | 0.3 | 0.3 | 0.2 | 0.2 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Three (2,4-di-t-butyl) phenyl-phosphite (phosphite ester kind antioxidant) | 0.1 | 0.1 | 0.1 | 0.1 | - | - | - | - | - |
| 2-(the tertiary octyl phenyl of 2'-hydroxyl-5'-) benzotriazole | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| The polymkeric substance of succinic acid and 4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine alcohols | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
performance test
1. adhesive property
By GB/T8808-88 test method, polyolefine packaging adhesive film in test the present invention and the cohesive force of different substrate materials, wherein the hot melt adhesive film of embodiment 1-6 tests adhesive property on aluminium flake, the hot melt adhesive film of embodiment 7 tests adhesive property on the glass sheet, the hot melt adhesive film of embodiment 8 tests adhesive property on PE film, and the hot melt adhesive film of embodiment 9 tests adhesive property on a pet film.
2. testing vapor transmission
By packaging adhesive film in laminating machine after heated lamination, test by standard GB/T 21529-2008, adopt electrolytic sensors method to measure water vapor transmittance (WVTR), test condition is 38 DEG C, 90% relative humidity.
3. volume specific resistance
By packaging adhesive film in laminating machine after heated lamination, by standard GB/T1410-2006 test volume resistivity.Test voltage is 100V, and the test duration is 120s.
The packaging adhesive film obtained by above-described embodiment, test its adhesive property, transmittance, water vapor transmittance and volume specific resistance as stated above, test result is in table 2.
Table 2: the traditional performance of each example
The result display of table 2: adopt the heat resistant type transparency polyolefin hot melt adhesive of the present invention program, have excellent optical property, electrical insulation capability and water vapor rejection performance, by grafting opposed polarity monomer, what can realize different substrate materials is effectively bonding.
4. creep test
By packaging adhesive film multiple-layer stacked in laminating machine after heated lamination, being made into test department bit width is 4mm, and thickness is the dumbbell shape sample of 2mm, tests tensile creep strain (%) by standard GB/T 11546.1-2008, test load is 10N, and test result is in table 3.
Table 3: the tensile creep strain result of each example
The result display of table 3: the heat resistant type transparency polyolefin hot melt adhesive adopting the present invention program, still has very excellent creep strength, have certain thermotolerance, meet service requirements under the high temperature of 110 DEG C.
These tests show that polyolefin hot-melt of the present invention can realize electrical insulation capability and the optical property of excellence, have certain thermotolerance and adhesive property, and maintain the physicals of polyolefine material excellence, chemical stability and good processibility.The service requirements in the field such as electronic equipment display screen and view port, solar module, mobile phone and tablet personal computer display screen (may use under hot and humid environment) under the electronic display of outdoor application and decoration, high temperature operation can be met.Therefore, the solution of the present invention has obvious superiority.
Above-mentioned embodiment is only the preferred embodiment of the present invention; can not limit the scope of protection of the invention with this, change and the replacement of any unsubstantiality that those skilled in the art does on basis of the present invention all belong to the present invention's scope required for protection.
Claims (6)
1. a heat resistant type transparency polyolefin hot melt adhesive, is characterized in that: it comprises following component by weight percentage
A) resin comprises:
Ethylene-l-octane copolymer 70-80%
Ethylene-propylene-1-butylene amorphous copolymer 10-25%;
Described resin also comprises the polyolefin plastomers of 5-20%; In described ethylene-l-octane copolymer, the molar content of octene is 20-50%, and fusing point is 40-80 DEG C, and weight-average molecular weight is 7000-9000;
B) radical initiator, its consumption accounts for the 0.01-0.7% of resin total mass;
C) grafted monomer, its consumption accounts for the 0.1-10% of total resin weight.
2. heat resistant type transparency polyolefin hot melt adhesive according to claim 1, is characterized in that: described grafted monomer is γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidoxypropyltrietandysilane andysilane, γ-(methacryloxy) propyl trimethoxy silicane, γ-Mercaptopropyltriethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl-acetic ester, tertiary ethylene carbonate, propionate, vinyl butyrate, maleat, maleic anhydride, itaconic anhydride, citraconic anhydride, allyl succinic anhydride, hexamethylene-4-alkene-1,2-dicarboxylic anhydride, 4-methylenecyclohex-4-alkene-1,2-dicarboxylic anhydride, dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboxylic anhydride, glycidyl allyl ether, vinyl glycidyl ether, toxilic acid glycidyl ester, glycidyl itoconate, glycidyl acrylate, glycidyl methacrylate, 2-tetrahydrobenzene-1-base glycidyl ether, tetrahydrobenzene-4,5-diglycidyl carboxylicesters, tetrahydrobenzene-4-glycidyl carboxylicesters, 5-norbornylene-2-methyl-2-glycidyl carboxylicesters, one or more mixing in interior-cis-bicyclo [2.2.1]-5-in heptan alkene-2,3-diglycidyl dicarboxylic ester.
3. heat resistant type transparency polyolefin hot melt adhesive according to claim 1, is characterized in that: the density of described ethylene-propylene-1-butylene amorphous copolymer is 0.85-0.91g/cm
3, ring and ball softening point is 80-140 DEG C.
4. heat resistant type transparency polyolefin hot melt adhesive according to claim 1, it is characterized in that: described radical initiator is 3, two (t-amyl peroxy) ethyl butyrate of 3-, 4, two (t-butyl peroxy) n-butyl pentanoate of 4-, 1, two (t-butyl peroxy)-3 of 1-, 5, 5-trimethyl-cyclohexane, 2, 5,-dimethyl-2, 5-pair-(t-butyl peroxy)-3-hexin, di-t-butyl peroxide, di t-amyl peroxide, t-butylcumylperoxide, two-(tert-butylperoxyiso-propyl) benzene, 2, 5-dimethyl-2, 5-pair-(t-butyl peroxy) hexane, one or more mixing in dicumyl peroxide.
5. heat resistant type transparency polyolefin hot melt adhesive according to claim 1, is characterized in that: it also comprises one or more in free radical activator, chainextender, fire retardant, photostabilizer, oxidation inhibitor, softening agent, tinting material or white dyes.
6. a preparation method for heat resistant type transparency polyolefin hot melt adhesive, is characterized in that it comprises the following steps:
According to claim 1 by each component premix evenly after, use twin screw extruder to carry out melting graft reaction at 160-200 DEG C, then cooled by device, through dicing machine granulation, re-use vulcanizer and be pressed into granular, sheet and membranaceous hot melt adhesive.
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