CN102560448B - Preparation method of composite microsphere containing dendritic structure polymer, anisotropic conductive material and anisotropic conductive film - Google Patents
Preparation method of composite microsphere containing dendritic structure polymer, anisotropic conductive material and anisotropic conductive film Download PDFInfo
- Publication number
- CN102560448B CN102560448B CN201010598248.4A CN201010598248A CN102560448B CN 102560448 B CN102560448 B CN 102560448B CN 201010598248 A CN201010598248 A CN 201010598248A CN 102560448 B CN102560448 B CN 102560448B
- Authority
- CN
- China
- Prior art keywords
- microballoon
- dendritic structure
- preparation
- anisotropic conductive
- polymkeric substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 46
- 239000004005 microsphere Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000004020 conductor Substances 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 125000000524 functional group Chemical group 0.000 claims abstract description 23
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- -1 amino, sulfydryl Chemical group 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 241000555268 Dendroides Species 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 24
- 239000002253 acid Substances 0.000 abstract description 18
- 238000007747 plating Methods 0.000 abstract description 12
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 11
- 230000002829 reductive effect Effects 0.000 abstract description 9
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 38
- 238000003756 stirring Methods 0.000 description 38
- 239000008367 deionised water Substances 0.000 description 29
- 229910021641 deionized water Inorganic materials 0.000 description 28
- 239000000243 solution Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000010907 mechanical stirring Methods 0.000 description 21
- 238000004140 cleaning Methods 0.000 description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 17
- 125000003368 amide group Chemical group 0.000 description 16
- 229910052737 gold Inorganic materials 0.000 description 16
- 239000010931 gold Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000004640 Melamine resin Substances 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 4
- 238000007306 functionalization reaction Methods 0.000 description 4
- 239000011806 microball Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 3
- 238000007098 aminolysis reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000000412 dendrimer Substances 0.000 description 3
- 229920000736 dendritic polymer Polymers 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- 229920006132 styrene block copolymer Polymers 0.000 description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 238000007265 chloromethylation reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229940117975 chromium trioxide Drugs 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- QJDXMNRUTJOBHS-UHFFFAOYSA-N 1-[dimethoxy(methyl)silyl]oxy-3-methylbut-3-en-2-one Chemical compound C(C(=C)C)(=O)CO[Si](OC)(OC)C QJDXMNRUTJOBHS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 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
- UUZBMBGPWXYEQZ-UHFFFAOYSA-N 5-amino-2-methylpent-2-enoic acid Chemical compound OC(=O)C(C)=CCCN UUZBMBGPWXYEQZ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- RPWFJAMTCNSJKK-UHFFFAOYSA-N Dodecyl gallate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 RPWFJAMTCNSJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229920006387 Vinylite Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JEOOVNWNJKBHRG-UHFFFAOYSA-N [Na+].[S--].[S--].[Au+3] Chemical compound [Na+].[S--].[S--].[Au+3] JEOOVNWNJKBHRG-UHFFFAOYSA-N 0.000 description 1
- UKKBVOHIFQOVRM-UHFFFAOYSA-N [Na].[B].[Cl] Chemical compound [Na].[B].[Cl] UKKBVOHIFQOVRM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- TWNDEXHSZJGRBX-UHFFFAOYSA-N boric acid;n-methylmethanamine Chemical compound CNC.OB(O)O TWNDEXHSZJGRBX-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 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
- 238000001723 curing Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N divinyl sulphide Natural products C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- 239000000555 dodecyl gallate Substances 0.000 description 1
- 235000010386 dodecyl gallate Nutrition 0.000 description 1
- 229940080643 dodecyl gallate Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229960004232 linoleic acid Drugs 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ZARXZEARBRXKMO-UHFFFAOYSA-N n,n-bis(ethenyl)aniline Chemical compound C=CN(C=C)C1=CC=CC=C1 ZARXZEARBRXKMO-UHFFFAOYSA-N 0.000 description 1
- KLDBIKVBMQMTGH-UHFFFAOYSA-N n,n-bis(ethenyl)prop-2-enamide Chemical compound C=CN(C=C)C(=O)C=C KLDBIKVBMQMTGH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses preparation methods of a composite microsphere containing dendritic structure polymer as well as an anisotropic conductive material and an anisotropic conductive film which respectively adopt the composite microsphere. The preparation method of the composite microsphere comprises the following steps: preparing an inner core of a high polymer and preparing at least one layer of metal conductive layer. At least one functional part is arranged between the inner core and the metal conductive layer, and the functional part is composed of a dendritic structure polymer and has functional groups. The functional part ensures that the microsphere can form the metal conductive layer without being corroded by high-concentration acid and an oxidant with heavy metal in the traditional coarsening method, thus the method of plating conductive metal is specifically simplified, and negative effects and pollution, which are caused by acid and heavy metal, to the environment are effectively reduced.
Description
Technical field
The present invention relates to the preparation method of electronic product, be specifically related to a kind of complex microsphere and adopt the anisotropic conductive material of this complex microsphere and the preparation method of anisotropic conductive film.
Background technology
The electrical connection field widespread use of anisotropic conductive material between the microelectrode of electronics, it mainly consists of insulating resin binding agent and the complex microsphere be dispersed in described insulating resin binding agent, complex microsphere wherein is most important, and complex microsphere generally is comprised of kernel and the conducting metal shell of insulation.The kernel of insulation is generally hydrophobicity, before formation conducting metal shell is as metallizing, must carry out alligatoring or hydrophilicity-imparting treatment to core surface, to improve the connectivity of metallic membrane and kernel.As the means that increase connectivity, be all the chromic acid that uses high density usually, the acid strong oxidizers such as sulfuric acid or permanganic acid.These strong acid oxygenants pollute greatly carrying capacity of environment, are not suitable for using.Even step, heavy metal that reduction clearing arranged in the process of metallizing residual can the minimizing by the metallizing finished product, are difficulties very but remove fully as chromium or manganese.
The Japan 61-64882 narration method of hydrophilizing little to carrying capacity of environment, such as using the finish materials coverage of synthetic resin that is selected from the energy adsorbing metals such as the unsaturated fatty acidss such as aminosilane based compound, diol compound, nitrile compound, titanate compound, butadiene polymer, linolic acid, linolenic acid, metal ion is attracted on this synthetic resins, and the method for then carrying out metallizing forms metal level on synthetic resins.But, in described method, when little microballoon is electroplated to particle diameter especially, be difficult to make metal level and synthetic resins intimate engagement.
China 200780011903 provides a kind of method of acid strong oxidizer of not using to manufacture conductive micro-balloons.First with melamine resin, the surface of microballoon is covered to processing, then hold metal being coated with on the microballoon of this melamine resin, then form metal level by plated by electroless plating.But not having suitable functional group, microballoon can't not form chemical bond with trimeric cyanamide, therefore melamine resin can not be bundled on microballoon, when needing to conduct electricity between two circuit elements that connect as be squeezed under additional stress, melamine resin and the metal plating on it easily peel off on microballoon.The formaldehyde that is usually used in addition making melamine resin is the reagent of known harm Environmental Health.
Therefore at present still very need one to the environment negative impact the little and simple method of step make conductive micro-balloons, especially microsphere surface is being added to the processing of layer modification, do not use high density strong acid and containing the requirement of heavy metal oxygenant thereby meet.
Summary of the invention
For addressing the above problem, the object of the present invention is to provide the method for the little making conduction complex microsphere of a kind of environmental pollution and negative impact, and the anisotropic conductive material and the anisotropic conductive film that adopt this conduction complex microsphere.
For achieving the above object, technical scheme of the present invention is: prepare a kind of method containing the dendritic structure polymer composite microsphere, described complex microsphere contain the high molecular polymer kernel and at least one deck metal conducting layer at the outermost layer of described complex microsphere, also be provided with at least one funtion part between this kernel and metal conducting layer, described funtion part forms and comprises the dendritic structure polymkeric substance and have functional group, and its preparation method comprises the following steps:
(1), prepare the polymer microballoon that predetermines composition and sphere diameter, i.e. described polymkeric substance kernel;
(2), with described polymer microballoon, carry out chemical reaction, synthetic at least one comprise the polymkeric substance outside of dendritic structure;
(3), the described polymer microballoon with at least one polymkeric substance outside is reacted with active agent, and at the outside functional group that forms of described polymer microballoon;
(4), the polymer microballoon containing functional group is contacted with chemical reagent, generate at least one deck metal conducting layer at described polymer microballoon outermost layer in its environment.
Preferably, in step (1) is carried out the polymerization single polymerization monomer reaction to described polymer microballoon, make described polymkeric substance core composition comprise that one or more contain the aromatic monomer of at least one unsaturated linkage.
Preferably, in step (1) is carried out the polymerization single polymerization monomer reaction to described polymer microballoon, make described polymkeric substance core composition comprise that one or more contain (methyl) acrylate monomer of at least one unsaturated linkage, and described (methyl) acrylate monomer can with the described aromatic monomer polymerization containing at least one unsaturated linkage.
Preferably, the outside formed described in step (2) comprises that the terminal of the dendroid branch of dendritic structure polymkeric substance has described functional group.
Preferably, described dendritic structure is to form branching on orderly branched structure again, the arrangement in synthesizing branched generation (Generation) so from generation to generation.
Preferably, the described functional group generated in step (3) comprises one or several in hydroxyl, carboxyl, amino, sulfydryl and triphenylphosphinyl.
A kind of preparation method of anisotropic conductive material, be dispersed in the insulating resin binding agent and make containing the dendritic structure polymer composite microsphere claimed in claim 1.
A kind of preparation method of anisotropic conductive film, make film by a kind of anisotropic conductive material claimed in claim 7.
Described containing the dendritic structure polymer composite microsphere, comprise high molecular polymer kernel and one deck metal conducting layer at least, also be provided with at least one funtion part between described kernel and metal conducting layer, described funtion part forms and comprises the dendritic structure polymkeric substance and have functional group.
Above-mentioned polymer microballoon is to prepare by polyreaction; Polyreaction comprises letex polymerization, emulsifier-free emulsion polymerization, micro-emulsion polymerization, mini-emulsion polymerization, dispersion polymerization, suspension polymerization and seeding polymerization.
The polyreaction suitable monomers is described as the entire chapter explanation, and one or more are containing the monomer of at least one unsaturated linkage.Suitable monomer may include two, three, four or more unsaturated linkages.As aromatic monomer containing at least one unsaturated linkage, and can with (methyl) acrylate monomer polymerization containing at least one unsaturated linkage.Suitable aromatic monomer is not limited only to vinylbenzene, p-chloromethyl styrene, Vinylstyrene, divinyl naphthalene, Phthalic acid, diallyl ester, N, N-divinyl aniline.Described as the disclosed patent of entire chapter, various polymerisable aromatic monomers within the scope of the present invention.
Suitable (methyl) esters of acrylic acid containing unsaturated linkage, be not limited only to (C2-C18) alkane chain diol two (methyl) acrylate.Particularly preferably multi-functional (methyl) acrylate monomer is (C2-C10) alkane chain diol two (methyl) acrylate, further preferred (C2-C8) alkane chain diol two (methyl) acrylate.Suitable (C2-C18) alkane chain diol two (methyl) acrylate includes but not limited to 1，2-ethandiol two (methyl) acrylate, 1,3-butyleneglycol two (methyl) acrylate, BDO two (methyl) acrylate, 1,5-pentanediol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,8-ethohexadiol two (methyl) acrylate and decamethylene-glycol two (methyl) acrylate.
Other monomer with functional group optional can with the monomer of (methyl) acrylate and aromatic monomer copolymerization.Suitable band functional group monomer includes but not limited to the dialkylene thioether, the vinyl sulfide sulfone, the divinyl acrylamide, triallyl (different) cyanurate, divinyl fourth diether, divinyl ether, diallyl maleate, allyl group acryloxy propionic ester, 2,2 '-bis-(4-(methyl) vinylformic acid propoxy-phenyl) propane, 2,2 '-bis-(4-(methyl) vinylformic acid diethoxy phenyl) propane, 1,2,4-benzene tricarboxylic acid triallyl, and allyl methacrylate(AMA).
Other particular monomers that are suitable for preparing functional polymer include but not limited to alpha-methyl styrene, the 4-1-chloro-4-methyl-benzene, the 4-nitrostyrolene, methyl acrylate, methyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, vinyl cyanide, vinyl pyrrolidone, glytidyl methacrylate, the methacrylic acid hydroxyethyl ester, the methacrylic dodecyl gallate, vinyl-acetic ester, vinylchlorid, divinyl, isoprene, Phthalic acid, diallyl ester, the methacryloyl methyltrimethoxy silane, methacryloxypropyl trimethoxy silane, the polyalkylene glycol methyl acrylate, 2-bromotrifluoromethane acrylate, 2-ethyl cyano group propernoic acid ester, methacrylic acid proyl ester, 2-methyl-2-vinylformic acid-2-sulphur ethyl ester, vinylformic acid, methacrylic acid, 2-methyl-2-vinylformic acid-2-(phosphonato) ethyl ester, 2-methyl-2-vinylformic acid-2-(phosphonato) propyl ester, 2-methyl-2-vinylformic acid-2-(phosphonato) butyl ester, phosphoric acid hydrogen two (methylacryoyloxyethyl) ester, the etheric acid methacrylic acid glycol ester, the acrylate caprolactone, 2-aminoethyl methylacrylic acid, 2-methyl-2-vinylformic acid-2-(4-morpholinyl) ethyl ester, dimethylaminoethyl acrylate methyl ammonia ethyl ester, acrylamide, Methacrylamide, tetramethylolmethane three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate etc., and above mixture.
This piece of described branch-shape polymer of explanation is the molecule that a kind of synthetic has special construction.Polymkeric substance is by the molecule be combined into little, relatively simple chemical monomer.In some cases, this combination is linear, in other cases, branch is arranged on chain or mutually link to form tridimensional network.It is described functional group that the terminal of dendroid branch has functional group, to form again branching on orderly branched structure, and the synthetic arrangement that is called branching generation (Generation) so from generation to generation.
The described branch-shape polymer of the disclosure is characterized in the Cong Yige center or claims original generation to start regular and neat repetition bifurcated, the tree structure of height of formation branching, have homogeneous 3-D solid structure and with the algebraically dependent geometrical property of branching.The description of relevant dendrimer is disclosed in the U.S. 4289872, the U.S. 4410688, and the U.S. 4507466.Its basic production process and method summary are at European Polymer Journal in recent years, and 2004, Volume 40, and Issue 7, Pages 1257-1281.
The described branch-shape polymer of this specification sheets comprises polymkeric substance, structure dendrimer, nucleocapsid dendrimer and the dendroid co-polymer of highly branched molecule, tree-shaped grafting.
Functionalization discloses described as entire chapter, refer to using chemical reagent to introduce the functionalization group by chemical reaction, chemical reagent used comprise any can with the polymer reaction in the microballoon outside, introduce the reagent of functionalization group, the functional group of introducing is such as fluorine, chlorine, bromine, iodine, amino, hydroxyl, sulfydryl, carboxyl, carboxylicesters or epoxy group(ing), or the combination of any above group.
Applicable chemical reagent for example, but is not limited to bischlormethyl ether, dihydroxymethyl amine, quadrol, hexanediamine-[1,6], tetramino methane, polyvinylamine, ammoniacal liquor, polyoxyethylene and derivative thereof.The functionalization group comprises single, two, and a plurality of groups or repeat or depend on the part of long-chain or short chain, as the oxyethyl group in oligopolymer or polyethylene oxide, amino in oligopolymer or polyvinylamine, hydroxyl in oligopolymer or polyvinyl alcohol, the vinyl mercapto of the sulfydryl in oligopolymer or polymerization etc.
Nuclear diameter is 0.01 μ m-1000 μ m in prepared polymkeric substance, and the diameter added after the above funtion part is 0.01 μ m-1000 μ m.But be not limited to above-mentioned size, according to actual needs, this size can be less than 0.01um or be greater than 1000um.
This piece of writing discloses described conducting metal, not special restriction, and applicable conducting metal includes but not limited to gold, silver, Bo ， Palladium, copper, iron, nickel, titanium, zinc, tin, aluminium, lead, cobalt, indium, cadmium, chromium, germanium, antimony, bismuth etc.; Also has alloy as nickel and phosphorus, silver and tin, copper and tin, lead and tin, the alloy that silver and plumbous and tin etc. are comprised of two or more metal.
Preferably, gold, silver, platinum, copper, nickel etc.
Above-mentioned conducting metal generally can be implemented by following gold-plated method.At first, the polymer microballoon cleaned can be used the strong oxidizing agent solution of high-concentration acidic wastewater carry out surface etching or be called alligatoring, thereby form fulcrum on polymer microballoon.Then the polymer microballoon after surface treatment or alligatoring can be immersed in the solution of tin protochloride and Palladous chloride, make the microsphere surface activation.So can on microballoon, form the fine nucleus of palladium catalyst.Subsequently, can use time phosphatization acid sodium, boron sodium-chlor, dimethyl amine borate, hydrazine etc. carry out reduction reaction, thereby form uniform palladium nucleus on microballoon.Then, the blapharoplast obtained is dispersed in plating solution, can use sodium hypophosphite to make the nickel salt reduction, form nickel coating on microballoon, then, in certain embodiments, the microballoon that is coated with nickel can be added in enough aurification plating liquors, change the reaction of plating or chemical gilding, thereby form Gold plated Layer at the outermost layer of microballoon.
The mentioned a kind of anisotropic conductive material of the present invention, comprise the insulating resin binding agent and be dispersed in complex microsphere as disclosed as this specification sheets in the insulating resin binding agent.Described complex microsphere, comprise high molecular polymer kernel and one deck metal conducting layer at least, also is provided with at least one funtion part between described kernel and metal conducting layer, and described funtion part is comprised of the dendritic structure polymkeric substance and has a functional group.
Resin in the technical program insulating resin binding agent, be not particularly limited, can be one or both and the two or more mixing in known resin, be the vinylites such as resin, vinyl chloride-based resin, acrylic resin, phenylethylene resin series such as vinyl acetate; The thermoplastic resins such as polyolefin-based resins, ethene one vinyl acetate between to for plastic resin copolymer, polyamide-based resin; Epoxy is that resin, polyurethane series resin, polyimide are that resin, unsaturated polyester are the curable resin that resin and they and its solidifying agent form; Styrene-butadiene one styrene block copolymer; Vinylbenzene one isoprene one styrene block copolymer, their thermoplastic block copolymers such as hydride; The elastic type such as styrene-butadiene copolymer rubber, neoprene, the fine styrene block copolymer rubber of propylene etc.The curing mode of curable resin comprises thermofixation, photocuring, ambient cure etc.One or more other additive is as organic solvent, antioxidant, and the Re Wending agent, the light temperature is determined agent etc. and also be can be used together as required.
The present invention also mentions a kind of anisotropic conductive film, comprises above-described a kind of anisotropic conductive material.Described anisotropic conductive material, comprise the insulating resin binding agent and be dispersed in complex microsphere as disclosed as this specification sheets in described insulating resin binding agent.Described complex microsphere, comprise high molecular polymer kernel and one deck metal conducting layer at least, also is provided with at least one funtion part between described kernel and metal conducting layer, and described funtion part is comprised of the dendritic structure polymkeric substance and has a functional group.
Content of the present invention described (methyl) acrylate comprises methacrylic ester and acrylate and their derivative; One micron is that μ m equals micron, and a nanometer is that nm equals part per billion meter.
Also it should be noted that, term used herein " comprises " clear and definite descriptive nature, number, and step, operation, or composition, but do not get rid of one or more character, number, step, operation, existence or the increase of composition and/or their combination.
Adopt the beneficial effect of the technical program to be: to the invention provides a kind of method and prepare complex microsphere and contain novel structure and application, also be provided with at least one funtion part between the kernel of this complex microsphere and metal conducting layer, described funtion part is comprised of the dendritic structure polymkeric substance and has a functional group, this dendritic structure polymers function partly makes the polymer microsphere need be by high density strong acid and the heavy metal etching processing of traditional method of roughening, just can carry out metallizing and form the homogeneous conductive metal level, concrete simplification the plating conducting metal method, and effectively reduce negative impact and the pollution to environment of strong acid and heavy metal.
Embodiment
Illustrate in greater detail the present invention below by embodiment.But scope of the present invention is not limited to these embodiment.
Embodiment 1,
Preparing 5 μ m body material microballoons is the polymkeric substance kernel of complex microsphere: the polystyrene seed aqueous suspension of getting 32.8g26.0% particle diameter 1.9 μ m, the 450g deionized water, 0.23g the 10% sodium dodecyl benzenylsulfonate aqueous solution joins in 2000mL four-hole round-bottomed flask, pass into nitrogen, stir post-heating to 60 ℃.Get the 15.0g Vinylstyrene, 135.0g vinylbenzene, the 10.7g 10% sodium dodecyl benzenylsulfonate aqueous solution, the 165g deionized water, stir with the homogeneous stirrer after mixing, and adds in the four-hole round-bottomed flask.Stir after 2 hours, cool to 40 ℃, add 0.2g 30% hydrogen peroxide.Get the 1.1g tertbutyl peroxide, the 0.3g10% sodium dodecyl benzenylsulfonate aqueous solution, the 65g deionized water, mix with the homogeneous stirrer and stir, and adds in the four-hole round-bottomed flask, then add the 56.3g20% polyvinylpyrrolidone aqueous solution, 25g deionized water.After 45 minutes, be heated to 60 ℃ 40 ℃ of stirrings.After 30 minutes, be heated to 65 ℃ 60 ℃ of stirrings.After 15 minutes, be heated to 70 ℃ 65 ℃ of stirrings.After thermopositive reaction, be heated to 90 ℃, continue to stir after 45 minutes, cooling flask to 25 ℃, filter to isolate the body material microballoon, i.e. the polymkeric substance kernel of complex microsphere, particle diameter 5 μ m.
Embodiment 2,
Chloromethylation embodiment 1 microballoon, at the outside chloromethyl that generates of microballoon: during the 10.0g microballoon in embodiment 1 and the anhydrous trichloromethane of 100mL are joined to the there-necked flask of 250mL, use mechanical stirring, microballoon is scattered in trichloromethane.The microballoon disperseed stirs (120rpm) 1 hour under 0 ℃, adds the 1.7mL anhydrous stannic chloride, after stirring 5 minutes, dropwise adds the 8.0mL chloromethyl ether.Dropwise, reaction system maintains 0 ℃ and stirs 30 minutes, then is warming up to 30 ℃ and continues to stir 3 hours.After reaction finishes, microballoon removes by filter solution with sand core funnel, and then microballoon is used the following solvent cleaning of 200mL successively: deionized water, 5% hydrochloric acid, deionized water, tetrahydrofuran (THF), ethanol, acetone.Microballoon after cleaning is the dry microballoon that had both obtained chloromethylation in 12 hours in 60 ℃ of baking ovens.
Embodiment 3,
Closure amination embodiment 2 microballoons, the dimethyl amido in original generation branch terminal introducing closure forms the not microballoon of branch: by 10.0g microballoon and the 140mLN in embodiment 2, dinethylformamide joins in the there-necked flask of 250mL, mechanical stirring is disperseed microballoon, add 25.0mL N, the N-dimethyl-ethylenediamine, system stirs 16 hours under 80 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, and then microballoon cleans with ethanol, acetone successively, and the microballoon after cleaning is the dry original generation closure amido branch terminal microballoon externally that both obtained in 12 hours in 60 ℃ of baking ovens.
Embodiment 4,
Protonated embodiment 3 microballoons, form positively charged original generation closure amido branch terminal microballoon externally: the 10.0g microballoon in embodiment 3 and 100mL deionized water are joined in the there-necked flask of 250mL, mechanical stirring is disperseed microballoon, dropwise add the 54.0mL36.5% concentrated hydrochloric acid, system stirs 3 hours under 15 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, with acetone, cleans after being washed till neutrality with deionized water again, and the microballoon after cleaning had both obtained protonated closure amido branch terminal microballoon externally of original generation after dry 12 hours in 60 ℃ of baking ovens.
Embodiment 5,
Prepare the tool closure amido dendritic structure microballoon externally of original generation with reductive agent: by the 10.0g microballoon in embodiment 4 and the anhydrous N of 100mL, dinethylformamide joins in the there-necked flask of 250mL, mechanical stirring is disperseed microballoon, 10.0g sodium borohydride divide 5 times, every 10 minutes, add, reinforced complete, system stirs 16 hours under 20 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, after being washed till neutrality with deionized water, with ethanol, acetone, clean successively, the microballoon after cleaning had both obtained the tool closure amido dendritic structure microballoon externally of original generation with reductive agent after dry 12 hours in 60 ℃ of baking ovens again.
Embodiment 6,
Form nm gold particles on the microballoon of embodiment 5: the 1.0g microballoon in embodiment 5 and 100mL deionized water are joined in the there-necked flask of 250mL, and mechanical stirring is disperseed microballoon, by 0.5g gold potassium chloride (KAuCl
4) be dissolved in the 50mL deionized water, dropwise add the tetra chlorauric acid potassium solution in flask, reinforced complete, system stirs 24 hours under 30 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, with deionized water, acetone, cleans successively, and the microballoon after cleaning had both obtained the microballoon that contains nm gold particles after dry 12 hours in 60 ℃ of baking ovens.
Embodiment 7,
Form the gold layer and overlay on embodiment 6 microballoons:
Get in the ultrasonic 50mL of the being dispersed in deionized water of embodiment 6 microballoon 1g that contains nm gold particles, be heated to 60 ℃, mechanical stirring also keeps 60 ℃, will contain the gold sodium sulfide (Na of 0.01M
3au (SO
3)
2) 0.32M S-WAT (Na
2sO
3), 0.08M Sulfothiorine (Na
2s
2o
3) and 0.32M sodium hydrogen phosphate (NaHPO
4), the gold plating liquid that the pH value is 9 adds with the speed of 10mL/min, after adding chemical gilding, continues mechanical stirring 4h under 60 ℃ of conditions.Then repeat to filter, fully wash by high-purity deionized water, obtain gold-plated complex microsphere.
Embodiment 8,
Amination embodiment 2 microballoons form first-generation dendritic structure microballoon externally: by 10.0g microballoon and the 140mLN in embodiment 2, dinethylformamide joins in the there-necked flask of 250mL, mechanical stirring is disperseed microballoon, add the 25.0mL quadrol, system stirs 16 hours under 80 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, and then microballoon cleans with ethanol, acetone successively, and the microballoon after cleaning is the dry aminated microballoon of the first-generation that both obtained in 12 hours in 60 ℃ of baking ovens.
Embodiment 9,
Esterified embodiment 8 microballoons form first-generation dendritic structure microballoon externally: the 10.0g microballoon in embodiment 8 and 120mL methyl alcohol are joined in the there-necked flask of 250mL, mechanical stirring is disperseed microballoon, add the 4.0g methyl acrylate, system stirs 16 hours under 50 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, and then microballoon cleans with ethanol, acetone successively, and the microballoon after cleaning is the dry first-generation dendritic structure microballoon externally that had both obtained esterification in 12 hours in 60 ℃ of baking ovens.
Embodiment 10,
Closure amination embodiment 9 microballoons, generate the microballoon of closure dimethyl amido in first-generation branch terminal: during the 10.0g microballoon in embodiment 9 and 120mL methyl alcohol are joined to the there-necked flask of 250mL, mechanical stirring is disperseed microballoon, add 10.0mLN, the N-dimethyl-ethylenediamine, system stirs 16 hours under 50 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, and then microballoon cleans with ethanol, acetone successively, and the microballoon after cleaning is the dry microballoon that had both obtained first-generation branch terminal tool closure dimethyl amido in 12 hours in 60 ℃ of baking ovens.
Embodiment 11,
Protonated embodiment 10 microballoons, form positively charged first-generation closure amido branch terminal microballoon externally: the 10.0g microballoon in embodiment 10 and 100mL deionized water are joined in the there-necked flask of 250mL, mechanical stirring is disperseed microballoon, dropwise add the 54.0mL36.5% concentrated hydrochloric acid, system stirs 3 hours under 15 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, with acetone, cleans after being washed till neutrality with deionized water again, and the microballoon after cleaning had both obtained the protonated closure amido branch terminal microballoon externally of the first-generation after dry 12 hours in 60 ℃ of baking ovens.
Embodiment 12,
The tool closure amido dendritic structure microballoon externally of preparation first-generation band reductive agent: by the 10.0g microballoon in embodiment 11 and the anhydrous N of 100mL, dinethylformamide joins in the there-necked flask of 250mL, mechanical stirring is disperseed microballoon, 10.0g sodium borohydride divide 5 times, every 10 minutes, add, reinforced complete, system stirs 16 hours under 20 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, after being washed till neutrality with deionized water, with ethanol, acetone, clean successively, the microballoon after cleaning had both obtained the tool closure amido dendritic structure microballoon externally of first-generation band reductive agent in 60 ℃ of baking ovens after dry 12 hours again.
Embodiment 13,
Form nm gold particles on the microballoon of embodiment 12: the 1.0g microballoon in embodiment 12 and 100mL deionized water are joined in the there-necked flask of 250mL, and mechanical stirring is disperseed microballoon, by 0.5g gold potassium chloride (KAuCl
4) be dissolved in the 50mL deionized water, dropwise add the tetra chlorauric acid potassium solution in flask, reinforced complete, system stirs 24 hours under 30 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, with deionized water, acetone, cleans successively, and the microballoon after cleaning had both obtained the microballoon that contains nm gold particles after dry 12 hours in 60 ℃ of baking ovens.
Embodiment 14,
Form the gold layer and overlay on embodiment 13 microballoons:
The microballoon that the gold plating method of repeated using embodiment 7 contains golden nanoparticle to embodiment 13 operates equally, obtains gold-plated microballoon.
Embodiment 15,
Aminolysis embodiment 9 microballoons, generate amido in first-generation branch terminal: during the 10.0g microballoon in embodiment 9 and 120mL methyl alcohol are joined to the there-necked flask of 250mL, mechanical stirring is disperseed microballoon, adds the 10.0mL quadrol, and system stirs 16 hours under 50 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, and then microballoon cleans with ethanol, acetone successively, and the microballoon after cleaning is the dry microballoon that had both obtained first-generation branch terminal band amino in 12 hours in 60 ℃ of baking ovens.
Embodiment 16,
Esterified embodiment 15 microballoons form s-generation dendritic structure: the 10.0g microballoon in embodiment 15 and 120mL methyl alcohol are joined in the there-necked flask of 250mL, and mechanical stirring is disperseed microballoon, adds the 8.0g methyl acrylate, and system stirs 16 hours under 50 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, and then microballoon cleans with ethanol, acetone successively, and the microballoon after cleaning is the dry s-generation dendritic structure microballoon that had both obtained esterification in 12 hours in 60 ℃ of baking ovens.
Embodiment 17,
Aminolysis embodiment 16 microballoons, generate amido in s-generation branch terminal: during the 10.0g microballoon in embodiment 16 and 120mL methyl alcohol are joined to the there-necked flask of 250mL, mechanical stirring is disperseed microballoon, adds the 20.0mL quadrol, and system stirs 16 hours under 50 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, and then microballoon cleans with ethanol, acetone successively, and the microballoon after cleaning is the dry microballoon that had both obtained s-generation branch terminal band amino in 12 hours in 60 ℃ of baking ovens.
Embodiment 18,
Esterified embodiment 17 microballoons form s-generation dendritic structure: the 10.0g microballoon in embodiment 17 and 120mL methyl alcohol are joined in the there-necked flask of 250mL, and mechanical stirring is disperseed microballoon, adds the 16.0g methyl acrylate, and system stirs 16 hours under 50 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, and then microballoon cleans with ethanol, acetone successively, and the microballoon after cleaning is the dry third generation dendritic structure microballoon that had both obtained esterification in 12 hours in 60 ℃ of baking ovens.
Embodiment 19,
Closure aminolysis embodiment 18 microballoons, the dimethyl amido that generates closure in third generation branch terminal no longer carries out branch: during the 10.0g microballoon in embodiment 18 and 120mL methyl alcohol are joined to the there-necked flask of 250mL, mechanical stirring is disperseed microballoon, add 20.0mLN, the N-dimethyl-ethylenediamine, system stirs 16 hours under 50 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, and then microballoon cleans with ethanol, acetone successively, and the microballoon after cleaning is the dry tool closure amido terminal third generation dendritic structure microballoon externally that both obtained in 12 hours in 60 ℃ of baking ovens.
Embodiment 20,
Protonated embodiment 19 microballoons, form positively charged third generation closure amido branch terminal microballoon externally: the 10.0g microballoon in embodiment 19 and 100mL deionized water are joined in the there-necked flask of 250mL, mechanical stirring is disperseed microballoon, dropwise add 54.0mL 36.5% concentrated hydrochloric acid, system stirs 3 hours under 15 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, with acetone, cleans after being washed till neutrality with deionized water again, and the microballoon after cleaning had both obtained the protonated closure amido branch terminal microballoon externally of the third generation after dry 12 hours in 60 ℃ of baking ovens.
Embodiment 21,
The tool closure amido dendritic structure microballoon externally for preparing third generation band reductive agent: by the 10.0g microballoon in embodiment 20 and the anhydrous N of 100mL, dinethylformamide joins in the there-necked flask of 250mL, mechanical stirring is disperseed microballoon, 10.0g sodium borohydride divide 5 times, every 10 minutes, add, reinforced complete, system stirs 16 hours under 20 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, after being washed till neutrality with deionized water, with ethanol, acetone, clean successively, the microballoon after cleaning had both obtained the tool closure amido dendritic structure microballoon externally of third generation band reductive agent in 60 ℃ of baking ovens after dry 12 hours again.
Embodiment 22,
Form nm gold particles on the microballoon of embodiment 21: the 1.0g microballoon in embodiment 21 and 100mL deionized water are joined in the there-necked flask of 250mL, and mechanical stirring is disperseed microballoon, by 0.5g gold potassium chloride (KAuCl
4) be dissolved in the 50mL deionized water, dropwise add the tetra chlorauric acid potassium solution in flask, reinforced complete, system stirs 24 hours under 30 ℃.After reaction finishes, microballoon removes by filter solution with sand core funnel, with deionized water, acetone, cleans successively, and the microballoon after cleaning had both obtained the microballoon that contains nm gold particles after dry 12 hours in 60 ℃ of baking ovens.
Embodiment 23,
Form the gold layer and overlay on embodiment 22 microballoons:
The microballoon that the gold plating method of repeated using embodiment 7 contains golden nanoparticle to embodiment 22 operates equally, obtains gold-plated microballoon.
Embodiment 24,
Alligatoring embodiment 1 microballoon uses chromium trioxide and sulfuric acid: the etching liquid 100ML that the chromium trioxide of preparation 0.5M and the sulfuric acid of 7.2M form, polydivinylbenezene/the phenylethylene micro ball that adds 10g embodiment 1 particle diameter 5 μ m, under normal temperature, ultrasonic dispersion is 30 minutes, then is warmed up to 60 ℃ of maintenances 30 minutes.Then repeat to filter, wash, obtain the microballoon through etching processing.
Embodiment 25,
Activation embodiment 24 microballoons: 1g embodiment 24 microballoons are joined in the aqueous solution of 20mL, on one side ultrasonic, stir 30 minutes on one side, microballoon is fully disperseed.Tin protochloride aqueous solution 20mL is joined in these slurries.The concentration of the aqueous solution of this tin protochloride is 20g/L, is heated to 40 ℃, stirs 10 minutes.Make tin ion be adsorbed onto microsphere surface and complete the sensitization processing.And then filtering solution, with the aqueous hydrochloric acid of 0.01M, clean.And then disperse with the aqueous hydrochloric acid of the 0.01M of 20mL, then add the Palladous chloride of the 1.5g/L of 20mL, be heated to 60 ℃, stir 10 minutes, carry out the activation treatment that microsphere surface catches palladium ion.And then filtering solution, use the washed with de-ionized water microballoon, again microballoon is distributed in the aqueous solution of 20mL, ultrasonic on one side, stir this slurries on one side, add the sodium hypophosphite of the 10g/L of 10mL simultaneously, keep 10min, complete the reduction of residue palladium ion, obtain the polydivinylbenezene/phenylethylene micro ball of activation.
Embodiment 26,
Form metal and overlay on embodiment 25 microballoons: the microballoon obtained after embodiment 25 activation is joined in the sodium citrate aqueous solution of the 100mL that contains 0.1M, sodium hydroxide with 0.1M after ultrasonic 30 minutes is adjusted pH value to 9, be heated to while stirring 40 ℃, stirring velocity is 150rpm.Then nickel ion being contained to liquid and reductive agent contains this liquid of liquid and joins in slurry with the speed of 1mL/min respectively.After the adding of two kinds of liquid, keep a stirring and maintain the temperature at 40 ℃, until no longer produce bubble.The single nickel salt that the formula that nickel ion contains liquid is 0.57M, the Trisodium Citrate of 0.1M.The formula that reductive agent contains liquid is sodium hypophosphite 1.40M, 2M sodium hydroxide.Thus, the microballoon with nickel-phosphor alloy coating obtained.Then gold-plated in surface enforcement by substitution method, then repeat to filter, fully wash by high-purity deionized water, obtain gold-plated complex microsphere.
Embodiment 27,
Alligatoring embodiment 1 microballoon uses hydrogen peroxide and sulfuric acid: the etching liquid 100mL that the hydrogen peroxide of preparation 3.2M and the sulfuric acid of 6M form, polydivinylbenezene/the phenylethylene micro ball that adds 10g embodiment 1 particle diameter 5 μ m, under normal temperature, ultrasonic dispersion is 5 minutes, then is warmed up to 60 ℃ of maintenances 180 minutes.Then repeat to filter, wash, obtain the microballoon through etching processing.
Embodiment 28,
Activation embodiment 27 microballoons: the method for then reusing embodiment 25 operates equally to embodiment 27 microballoons, obtains the polydivinylbenezene/phenylethylene micro ball of activation.
Embodiment 29,
Form metal and overlay on embodiment 28 microballoons: the microballoon that the method for plating metal of repeated using embodiment 26 obtains after embodiment 28 is activated operates equally, obtains gold-plated microballoon.
Embodiment 30,
Analyze gold-plated microballoon heavy metal content: respectively get 3g embodiment 7,14,23,26 and 29 microballoons covered with gold leaf, add respectively the mixing acid of 60mL concentrated hydrochloric acid and nitric acid, heating, dissolve metallic microspheres fully while stirring.The solution that takes a morsel dilutes by high-purity deionized water, then uses inductive coupling plasma emission spectrograph (Inductively Coupled Plasma-Atomic Emission Spectrometer) to detect the chromium element.
Sum up preparation process whether use high density strong acid and results of elemental analyses as follows:
Adopt the beneficial effect of the technical program to be: also to be provided with at least one layer function part between kernel and metal conducting layer, described funtion part is comprised of the dendritic structure polymkeric substance and has a functional group, this dendritic structure with functional group partly makes conducting metal to form thereon, needn't use the high density strong acid of traditional method of roughening and contain heavy metal oxygenant etching processing, thereby concrete simplification the method for plating conducting metal, and effectively reduce acid and heavy metal to negative impact and the pollution of environment.
Embodiment 31,
A kind of anisotropic conductive material, comprise the insulating resin binding agent and be dispersed in the complex microsphere in described insulating resin binding agent.The preparation method of described complex microsphere is identical with embodiment 14 and 23.Component and the preparation method of described resin adhesive belong to known technology, as described in patent documentation JP200580022240.0, do not repeat them here.
Embodiment 32,
A kind of anisotropic conductive film, comprise anisotropic conductive material and anisotropic conducting film.The preparation method of described anisotropic conductive material is identical with embodiment 31.Described film forming method is known technology, does not repeat them here.
In above-described embodiment, because core parts are complex microsphere of the present invention, it has exclusive funtion part, described funtion part is comprised of the dendritic structure polymkeric substance and has a functional group, make conductive metal layer can be formed on the dendritic structure polymkeric substance, not only can meet good conduction application requiring, and preparation need be with the dense strong acid of traditional method of roughening with containing heavy metal oxygenant etching processing, just can form conductive metal layer, thereby concrete simplification the plating conducting metal method, and effectively reduce negative impact and the pollution to environment of acid and heavy metal.
Above-described is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, without departing from the concept of the premise of the invention, can also make some distortion and improvement, and these all belong to protection scope of the present invention.
Claims (7)
1. the preparation method containing the dendritic structure polymer composite microsphere, described complex microsphere contains a polymkeric substance kernel and at least one functionalized polymer outside, and have that at least one deck metal conducting layer is at the outermost layer of described complex microsphere, its preparation method comprises the following steps:
(1), prepare the polymer microballoon that predetermines composition and sphere diameter, i.e. described polymkeric substance kernel;
(2), with described polymer microballoon, carry out chemical reaction, synthetic at least one comprise the polymkeric substance outside of dendritic structure;
(3), the described polymer microballoon with at least one polymkeric substance outside is reacted with active agent, and at the outside functional group that forms of described polymer microballoon;
(4), the polymer microballoon containing functional group is contacted with chemical reagent, generate at least one deck metal conducting layer at described polymer microballoon outermost layer in its environment;
Wherein, described dendritic structure is to form branching on orderly branched structure again, so arrangement in synthesizing branched generation from generation to generation.
2. the preparation method containing the dendritic structure polymer composite microsphere as claimed in claim 1, in step (1) is carried out the polymerization single polymerization monomer reaction to described polymer microballoon, make described polymkeric substance core composition comprise that one or more contain the aromatic monomer of at least one unsaturated linkage.
3. the preparation method containing the dendritic structure polymer composite microsphere as claimed in claim 2, in step (1) is carried out the polymerization single polymerization monomer reaction to described polymer microballoon, make described polymkeric substance core composition comprise that one or more contain (methyl) acrylate monomer of at least one unsaturated linkage, and described (methyl) acrylate monomer can with the described aromatic monomer polymerization containing at least one unsaturated linkage.
4. the preparation method containing the dendritic structure polymer composite microsphere as claimed in claim 1, the outside formed described in step (2) comprises that the terminal of the dendroid branch of dendritic structure polymkeric substance has described functional group.
5. the preparation method containing the dendritic structure polymer composite microsphere as claimed in claim 1, the described functional group generated in step (3) comprises one or several in hydroxyl, carboxyl, amino, sulfydryl and triphenylphosphinyl.
6. the preparation method of an anisotropic conductive material, is characterized in that, by claimed in claim 1, containing the dendritic structure polymer composite microsphere, be dispersed in the insulating resin binding agent and make.
7. the preparation method of an anisotropic conductive film, is characterized in that, a kind of anisotropic conductive material claimed in claim 6 is made to film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010598248.4A CN102560448B (en) | 2010-12-21 | 2010-12-21 | Preparation method of composite microsphere containing dendritic structure polymer, anisotropic conductive material and anisotropic conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010598248.4A CN102560448B (en) | 2010-12-21 | 2010-12-21 | Preparation method of composite microsphere containing dendritic structure polymer, anisotropic conductive material and anisotropic conductive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102560448A CN102560448A (en) | 2012-07-11 |
| CN102560448B true CN102560448B (en) | 2014-01-08 |
Family
ID=46407008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010598248.4A Active CN102560448B (en) | 2010-12-21 | 2010-12-21 | Preparation method of composite microsphere containing dendritic structure polymer, anisotropic conductive material and anisotropic conductive film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102560448B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989508B (en) * | 2012-11-21 | 2015-12-09 | 北京大学深圳研究生院 | The preparation method and use of the Pd nano particle that a kind of polymer microballoon is immobilized |
| CN102990062B (en) * | 2012-12-17 | 2014-07-23 | 苏州纳微科技有限公司 | Method for preparing composite microsphere |
| CN103182515B (en) * | 2013-03-22 | 2015-04-08 | 中国科学院上海应用物理研究所 | Precious metal composite material and precious metal micro-nano material, and preparation methods thereof |
| CN105478752B (en) * | 2015-12-14 | 2017-10-24 | 东华大学 | A kind of preparation method of micrograde polymer base composite conducting gold goal |
| WO2020095796A1 (en) * | 2018-11-07 | 2020-05-14 | 日本化学工業株式会社 | Coated particle, electrically conductive material comprising same, and method of manufacturing coated particle |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4289872A (en) * | 1979-04-06 | 1981-09-15 | Allied Corporation | Macromolecular highly branched homogeneous compound based on lysine units |
| CN1340573A (en) * | 2000-07-13 | 2002-03-20 | 三井武田化学株式会社 | Multi-layer structure conductive resin granule and anisotropic conductive adhesive made up by its use |
| CN102136313A (en) * | 2010-12-06 | 2011-07-27 | 苏州纳微生物科技有限公司 | Compound microsphere, anisotropic conductive material, anisotropic conductive film and conductive structure |
-
2010
- 2010-12-21 CN CN201010598248.4A patent/CN102560448B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4289872A (en) * | 1979-04-06 | 1981-09-15 | Allied Corporation | Macromolecular highly branched homogeneous compound based on lysine units |
| CN1340573A (en) * | 2000-07-13 | 2002-03-20 | 三井武田化学株式会社 | Multi-layer structure conductive resin granule and anisotropic conductive adhesive made up by its use |
| CN102136313A (en) * | 2010-12-06 | 2011-07-27 | 苏州纳微生物科技有限公司 | Compound microsphere, anisotropic conductive material, anisotropic conductive film and conductive structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102560448A (en) | 2012-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102560448B (en) | Preparation method of composite microsphere containing dendritic structure polymer, anisotropic conductive material and anisotropic conductive film | |
| JP5879686B2 (en) | Method for producing core-shell particles, core-shell particles, paste composition using the same, and sheet composition | |
| JP5650611B2 (en) | Anisotropic conductive film, method for manufacturing anisotropic conductive film, connection method, and joined body | |
| CN102136314B (en) | Preparation method of composite microspheres, anisotropy conducting material and anisotropy conducting film | |
| CN100544551C (en) | The manufacture method of conductive pattern material | |
| CN102990062B (en) | Method for preparing composite microsphere | |
| KR20150083934A (en) | Catalyst for electroless plating, metallic coating film produced using same, and method for producing said metallic coating film | |
| KR101454194B1 (en) | Conductive microparticle, resinparticle, and anisotropic conductive material using same | |
| JP5785238B2 (en) | Conductive fine particles | |
| JP2006269296A (en) | Manufacturing method of particle with protrusions, particle with protrusions, conductive particle with protrusions, and anisotropic conductive material | |
| CN102199407B (en) | High-dispersing nanometer silver and high-performance conductive adhesive | |
| CN102167838B (en) | Polymer composite microsphere containing dendritic structure, anisotropic conducting material and anisotropic conducting film | |
| CN102977395B (en) | Preparation method of conductive material-made composite microsphere | |
| JP4412669B2 (en) | Coated conductive particles, conductive material, anisotropic conductive adhesive, and anisotropic conductive joint structure | |
| CN102136313B (en) | Compound microsphere, anisotropic conductive material, anisotropic conductive film and conductive structure | |
| CN108604481A (en) | Insulation-coated electroconductive particles, anisotropic conductive adhesive and connection structural bodies | |
| KR20160135295A (en) | Resin particles, conductive microparticles, and anistropic conductive material using same | |
| JP4957871B2 (en) | Crosslinked polymer particles and method for producing the same | |
| CN105694593B (en) | A kind of printing ink composition and the method using its formation conductive layer | |
| CN103680765B (en) | A kind of conductive composite microsphere preparation method of environment-friendly type | |
| JP5796232B2 (en) | Conductive particles, anisotropic conductive materials, and connection structures | |
| CN103302301A (en) | Novel method for preparing C/Ag composite nanomaterial with controllable Ag coating layer thickness | |
| WO2007072912A1 (en) | Conductive fine particle and anisotropic conductive material | |
| JP2005036265A (en) | Electroconductive particles, electroconductive material and anisotropic electroconductive layer | |
| CN105176266A (en) | Conductive plastic paint with electromagnetic shielding effect and preparation method of conductive plastic paint |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: SUZHOU NANO-MICRO TECHNOLOGY CO., LTD. Free format text: FORMER NAME: SUZHOU NANO-MICRO BIO-TECHNOLOGY CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: Xinghu Street Industrial Park of Suzhou city in Jiangsu province 215000 No. 218 BioBAY building C1 Patentee after: SUZHOU NANOMICRO TECHNOLOGY Co.,Ltd. Address before: Xinghu Street Industrial Park of Suzhou city in Jiangsu province 215000 No. 218 BioBAY building C1 Patentee before: Suzhou Nano-Micro Technology Co.,Ltd. |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No. 2, Bai Sichuan street, Suzhou Industrial Park, Jiangsu Province Patentee after: SUZHOU NANOMICRO TECHNOLOGY Co.,Ltd. Address before: 215000 C1 Biological Park, No. 218 Xing Hu Street, Suzhou Industrial Park, Jiangsu. Patentee before: SUZHOU NANOMICRO TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231102 Address after: Room 502, building 10, Northwest District, Suzhou nano City, 99 Jinjihu Avenue, Suzhou Industrial Park, 215000, Jiangsu Province Patentee after: Suzhou Xindao Electronic Technology Co.,Ltd. Address before: No. 2, Bai Sichuan street, Suzhou Industrial Park, Jiangsu Province Patentee before: SUZHOU NANOMICRO TECHNOLOGY Co.,Ltd. |