CN100425668C - Flame retardant adhesive without halogen in use for flexible printed circuit - Google Patents
Flame retardant adhesive without halogen in use for flexible printed circuit Download PDFInfo
- Publication number
- CN100425668C CN100425668C CNB2006101244564A CN200610124456A CN100425668C CN 100425668 C CN100425668 C CN 100425668C CN B2006101244564 A CNB2006101244564 A CN B2006101244564A CN 200610124456 A CN200610124456 A CN 200610124456A CN 100425668 C CN100425668 C CN 100425668C
- Authority
- CN
- China
- Prior art keywords
- flexible printed
- printed circuit
- ester
- phosphate
- parts
- 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.)
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- 229910052736 halogen Inorganic materials 0.000 title claims description 31
- 150000002367 halogens Chemical class 0.000 title claims description 30
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 22
- 239000003063 flame retardant Substances 0.000 title abstract description 22
- 239000000853 adhesive Substances 0.000 title abstract description 19
- 230000001070 adhesive effect Effects 0.000 title abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 238000004132 cross linking Methods 0.000 claims abstract description 12
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 34
- -1 allyl group phosphate ester Chemical class 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 150000002148 esters Chemical class 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 235000010985 glycerol esters of wood rosin Nutrition 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000011889 copper foil Substances 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 239000010452 phosphate Substances 0.000 claims description 13
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 11
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012764 mineral filler Substances 0.000 claims description 10
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 7
- 239000000347 magnesium hydroxide Substances 0.000 claims description 7
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 7
- 239000004160 Ammonium persulphate Substances 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 5
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N isopropyl-benzene Natural products CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical group [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 3
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000005030 aluminium foil Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229920006267 polyester film Polymers 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 claims description 3
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 claims description 3
- 229940113124 polysorbate 60 Drugs 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 229960001708 magnesium carbonate Drugs 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 16
- 239000000839 emulsion Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- DZMOLBFHXFZZBF-UHFFFAOYSA-N prop-2-enyl dihydrogen phosphate Chemical compound OP(O)(=O)OCC=C DZMOLBFHXFZZBF-UHFFFAOYSA-N 0.000 abstract 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 239000011256 inorganic filler Substances 0.000 abstract 1
- 229910003475 inorganic filler Inorganic materials 0.000 abstract 1
- 239000011229 interlayer Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 14
- 239000000758 substrate Substances 0.000 description 12
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004812 Fluorinated ethylene propylene Substances 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 241000498779 Myristica Species 0.000 description 1
- 235000009421 Myristica fragrans Nutrition 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- XMNQCSOOUOJOLR-UHFFFAOYSA-N ethyl methyl hydrogen phosphate Chemical compound CCOP(O)(=O)OC XMNQCSOOUOJOLR-UHFFFAOYSA-N 0.000 description 1
- NMCWERWDCXNTLB-UHFFFAOYSA-N ethyl phenyl hydrogen phosphate Chemical compound CCOP(O)(=O)OC1=CC=CC=C1 NMCWERWDCXNTLB-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
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- 239000001702 nutmeg Substances 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920009441 perflouroethylene propylene Polymers 0.000 description 1
- BSMFIANCGKWVPR-UHFFFAOYSA-N phosphoric acid propylbenzene Chemical compound P(O)(O)(O)=O.C(CC)C1=CC=CC=C1 BSMFIANCGKWVPR-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 235000016804 zinc Nutrition 0.000 description 1
Abstract
This invention discloses a method for preparing halogen-free and flame-retardant acrylate adhesive for flexible printing circuit board. The adhesive comprises: multiple acrylate monomers, allyl phosphate, crosslinking monomer, initiator, emulsifier, phosphorus-containing filler and inorganic filler. The method comprises: (1) adding multiple acrylate monomers, allyl phosphate, crosslinking monomer, initiator and emulsifier into a reactor; (2) adding deionized water, heaing and polymerizing under stirring to synthesize an emulsion; (3) adding the fillers into the emulsion to obtain the halogen-free and flame-retardant acrylate adhesive. The adhesive can be used for interlayer adhering of multi-layered flexible printing circuit board, and the obtained flexible printing circuit board has such adadvantages as good flame retardancy, high peel strength, good Sn weldability and good synthetic properties.
Description
Technical field
The present invention relates to a kind of prescription and the application of this tackiness agent on the flexible printed circuit base material of acrylate multiple copolymer flame retardant adhesive without halogen.
Technical background
Nowadays, printed circuit board is widely used in the every field, all comprises corresponding printed circuit board in nearly all electronics.Adopt the flexible printed-circuit board can reduced volume, realize advantages such as product is thin, light, little, therefore the high-tech electronic products such as automobile satellite direction locating device, Digital Video, folding cell phone and LCD TV that emerge have in recent years all adopted flexible printed-circuit board in a large number.
The flame retardant resistance that improves printed circuit board is the safety that guarantees whole electronic system or equipment, a very important aspect that prolongs its work-ing life.Can set about improving the flame retardant resistance of printed circuit board in the production of reality aspect a lot, be wherein a kind of important channel as what use flame-retarding adhesive in the printed electronic circuit base board.
When making flexible printed-circuit board, the most frequently used method of flame retardant resistance that improves tackiness agent is to use and brominatedly waits the resin of halogen and add synergist such as antimonous oxide.This class tackiness agent flame retardant effect is good, but the time can produce hydrogen halide with dioxin, furans toxic substance pollute environment in burning.The work that the flexible printed-circuit board substrate sticks with glue the agent halogen-free flameproof also has to be carried out, but the major part of using is an epoxy-resin systems.For example patent of invention CN1670107A has used the various phosphorous epoxy resins of formation such as reactive phosphorus compound H CA, and patent of invention CN1449427A has used the halogen-free epoxy resin that adds crosslinked phenyl phosphazene compound.
Summary of the invention
Purpose of the present invention is exactly the demand that sticks with glue the agent halogen-free flameproof at the flexible printed-circuit board substrate, a kind of prescription of acrylate multiple copolymer flame retardant adhesive without halogen is provided and uses good flame resistance, stripping strength height, the anti-tin-welding of this tackiness agent preparation good, and the flexible printed circuit base material of better comprehensive performance is arranged.
Realize that the object of the invention technical scheme is:
A kind of flexible printed circuit is an acrylate multiple copolymer flame retardant adhesive without halogen with non-halogen flame-proof acrylic ester gum stick, this tackiness agent comprises multicomponent methacrylate monomer, allyl group phosphoric acid ester, cross-linking monomer, reaction initiator, emulsifying agent, solidifying agent, phosphorous filler and mineral filler component, and its composition ratio of quality and the number of copies is:
100 parts of multicomponent methacrylate comonomers,
5～40 parts of allyl group phosphate ester monomers,
1～10 part of cross-linking modified monomer,
100～500 parts of deionized waters,
1～10 part of reaction initiator,
1～10 part of emulsifying agent,
10～60 parts of phosphorous fillers,
10～50 parts of mineral fillers,
Better composition ratio of quality and the number of copies is:
100 parts of multicomponent methacrylate comonomers
10～30 parts of allyl group phosphate ester monomers
5～10 parts of cross-linking modified monomers
150～300 parts of deionized waters
2～6 parts of reaction initiators
2～7 parts of emulsifying agents
20～30 parts of phosphorous fillers
20～40 parts of mineral fillers
The multicomponent methacrylate comonomer that uses among the present invention is one or more the mixture in alkyl acrylate, alkyl methacrylate, vinylbenzene, vinyl cyanide, the vinyl acetate.Methacrylic acid C preferably
1～C
8Alkyl ester and vinyl cyanide.
The allyl group phosphate ester monomer that uses among the present invention is one or more the mixture in allyl group phosphate dialkyl ester, allyl group di(2-ethylhexyl)phosphate aromatic ester and the allyl group aryl phosphate alkyl ester.Allyl group di(2-ethylhexyl)phosphate C preferably
1～C
8Alkyl ester.
The cross-linking modified monomer that uses among the present invention is methacrylic acid, vinylformic acid, methacrylic acid β-C
2～C
8Hydroxy ester, propenoic acid beta-C
2～C
8In hydroxy ester, acrylamide, Methacrylamide and the glycidyl acrylate two or more contains the mixture of different crosslinked groups.Preferably methacrylic acid and propenoic acid beta-C
2～C
8Hydroxy ester.
The reaction initiator that uses among the present invention is 2-(tertiary butyl azo) butyronitrile, 2,2 '-2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2 '-one or more mixture in Diisopropyl azodicarboxylate, dilauroyl peroxide, dibenzoyl peroxide, Potassium Persulphate and the ammonium persulphate.Preferably 2,2 '-Diisopropyl azodicarboxylate and ammonium persulphate.
The emulsifying agent that uses among the present invention is in the positive alkyl sodium sulfate salt of anionic, positive mersolates, glycerine single-hard ester acid ester and the alkylaryl sulphonate one or more, contains one or more mixture in octyl phenol polyoxy ethenol system row, polysorbate60, tween 80, polysorbas20, class of department 80 and the class of department 65 of oxyethane with the OP-10 of nonionic class etc.Sodium laurylsulfonate and contain the octyl phenol polyoxy vinyl alcohol OP-10 of 10 moles of ethylene oxide preferably.
The phosphorous filler that uses among the present invention is one or more the mixture in triethyl phosphate, tributyl phosphate, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate biphenyl ester and the tricresyl phosphate isopropyl benzene ester.The lower triphenylphosphate of price preferably.
The mineral filler of using among the present invention is one or more the mixture in silicon-dioxide, aluminum oxide, talcum, lime carbonate, magnesiumcarbonate, zinc borate, zinc oxide, potassium titanate, silicon nitride, boron nitride, aluminium hydroxide and the magnesium hydroxide.Preferably silicon-dioxide and magnesium hydroxide.
Non-halogen flame-proof acrylic ester gum stick of the present invention is applied in the flexible printed circuit, and the electric insulating film of use is a kind of in Kapton, polyester film, poly (ether ether ketone) film and the fluorinated ethylene propylene film.Preferred Kapton.Film thickness depends on needs, in preferred 12.5 microns-50 microns scope.
The conductor layer that uses in flexible printed circuit is the alloy of stainless steel, copper, aluminium, nickel, chromium, tungsten, titanium, zinc or these metals.Preferably rolled copper foil or electrolytic copper foil.The thickness of Copper Foil is not limit, and the thickness of preferred Copper Foil is 12 microns-50 microns.
Flexible printed circuit of the present invention is with non-halogen flame-proof acrylic ester gum stick---the synthetic method and the synthesis step of multi-component copolymer acrylate flame retardant adhesive without halogen are:
Step 1, the multicomponent methacrylate monomer with selected, allyl group phosphate ester monomer, cross-linking monomer, reaction initiator, emulsifying agent, deionized water add to have in heating, stirring, backflow, the thermometric reactor in described ratio and mix;
Step 2, feeding nitrogen stir, and control reaction temperature was reacted 1～24 hour between 40 ℃～150 ℃, and discharging is filtered in cooling;
Step 3, add phosphorous filler, mineral filler, mix, keeping the solid content mass percent is 15%～40% promptly to get described tackiness agent
In the synthesis step 2 of described multi-component copolymer acrylate flame retardant adhesive without halogen, best temperature of reaction is 60 ℃～120 ℃, and the best reaction times is 3～8 hours.
The application method of prepared tackiness agent in the flexible printed circuit substrate is:
Above-mentioned glue evenly is coated in the one side of electric insulating film (as polyimide or polyester film), thick 10 microns～40 microns of glue, preliminary drying is 30～60 minutes in 80 ℃～120 ℃ baking oven, the compound tinsel (Copper Foil or aluminium foil) that goes up, in the composite pressure machine in 120 ℃～200 ℃, 20～60 kg/cm
2Under the pressure, kept 20～180 minutes, promptly make the flexible printed circuit substrate.Preferred combined temp is that 150 ℃～180 ℃, pressure are 30～50 kg/cm
2, the time is 60～120 minutes.
Prepared flexible printed circuit substrate records stripping strength 〉=1.4 Newton/millimeter according to the testing method of UL-94 standard, IPC-TM-650, anti-tin-welding is not stratified after 288 ℃, 10 seconds, non-foaming in the tin bath, flame retardant resistance reaches the UL94V-0 level, surface resistivity 〉=1.0 * 10
5M Ω, volume resistance 〉=1.0 * 10
6M Ω m.
Above-mentioned material all is commercially available products.
Advantage of the present invention is:
1. tackiness agent is the liquid single packing, and grow, never degenerated in 12 months storage period;
2. tackiness agent is an aq. type, solvent-free volatilization and pollution;
3. not halogen-containingly in the tackiness agent just can reach good flame retardant effect.
Embodiment
The present invention further specifies with following example, but the present invention is not limited to these examples.
Embodiment 1
Get butyl methacrylate 100 grams, methyl methacrylate 40 grams, vinyl cyanide 40 grams, allyl group dibutyl phosphate 40 grams, methacrylic acid 10 grams, glycidyl methacrylate 10 grams, 2,2 '-Diisopropyl azodicarboxylate 5 grams, sodium laurylsulfonate 4 grams and OP-106 gram deionized water 600 grams, reflux is 4 hours in 2000 milliliters of four-hole boiling flasks that have agitator, prolong, thermometer, the cooling, filter the multi-component copolymer acrylate emulsion.Add triphenylphosphate 40 grams, magnesium hydroxide 45 grams mix, and promptly get flame retardant adhesive without halogen in use for flexible printed circuit of the present invention.
The tackiness agent that makes is evenly coated in the one side of the Kapton of 25 micron thickness, and preliminary drying is 30 minutes in 115 ± 5 ℃ baking oven, is cooled to room temperature.Superimposed with the electrolytic copper foil of 35 micron thickness, in the composite pressure machine in 170 ℃, 50 kg/cm
2Under the pressure, kept 90 minutes, promptly get described flexible printed circuit substrate.
Embodiment 2
Get ethyl propenoate 50 grams, vinylformic acid pentyl ester 20 grams, vinyl cyanide 15 grams, allyl group phosphoric acid propyl group phenyl ester 15 grams, vinylformic acid 3 grams, Methacrylamide 3 grams, ammonium persulphate 2 grams, dodecyl sulphate potassium 2 grams and polysorbate60 3 grams, deionized water 300 grams, reflux is 8 hours in 1000 milliliters of four-hole boiling flasks that have agitator, prolong, thermometer, the cooling, filter the multi-component copolymer acrylate emulsion.Add triethyl phosphate 20 grams, aluminium hydroxide 20 grams mix, and promptly get flame retardant adhesive without halogen in use for flexible printed circuit of the present invention.
The tackiness agent that makes is evenly coated in the one side of the Kapton of 12.5 micron thickness, and preliminary drying is 60 minutes in 80 ± 5 ℃ baking oven, is cooled to room temperature.Superimposed with the electrolytic copper foil of 12 micron thickness, in the composite pressure machine in 180 ℃, 30 kg/cm
2Under the pressure, kept 60 minutes, promptly get described flexible printed circuit substrate.
Embodiment 3
Get vinylbenzene 40 grams, propyl methacrylate 10 grams, vinyl acetate 8 grams, allyl group phosphoric acid methyl ethyl ester 10 grams, glycidyl acrylate 2 grams, Methacrylamide 2 grams, dibenzoyl peroxide 1 gram, Sodium Lauryl Sulphate BP/USP 0.5 gram and class of department 802.5 grams, deionized water 200 grams, reflux is 12 hours in 500 milliliters of four-hole boiling flasks that have agitator, prolong, thermometer, the cooling, filter the multi-component copolymer acrylate emulsion.Add Tritolyl Phosphate 10 grams, silicon-dioxide 5 grams mix, and promptly get flame retardant adhesive without halogen in use for flexible printed circuit of the present invention.
The tackiness agent that makes is evenly coated in the one side of the Kapton of 50 micron thickness, and preliminary drying is 40 minutes in 100 ± 5 ℃ baking oven, is cooled to room temperature.Superimposed with the electrolytic copper foil of 50 micron thickness, in the composite pressure machine in 150 ℃, 40 kg/cm
2Under the pressure, kept 120 minutes, promptly get described flexible printed circuit substrate.
Embodiment 4
Get N-Hexyl methacrylate 100 grams, methyl acrylate 40 grams, vinyl cyanide 40 grams, allyl group phosphoric acid methyl polyhexamethylene 40 grams, methacrylic acid 10 grams, glycidyl acrylate 10 grams, 2-(tertiary butyl azo) butyronitrile 5 grams, nutmeg base sodium sulfonate and polysorbas20 be totally 10 grams, deionized water 600 grams, reflux is 5 hours in 2000 milliliters of four-hole boiling flasks that have agitator, prolong, thermometer, the cooling, filter the multi-component copolymer acrylate emulsion.Add triphenylphosphate 40 grams, magnesium hydroxide 45 grams mix, and promptly get flame retardant adhesive without halogen in use for flexible printed circuit of the present invention.
The tackiness agent that makes is evenly coated in the one side of the Kapton of 50 micron thickness, and preliminary drying is 40 minutes in 100 ± 5 ℃ baking oven, is cooled to room temperature.Superimposed with the electrolytic copper foil of 35 micron thickness, in the composite pressure machine in 120 ℃, 35 kg/cm
2Under the pressure, kept 40 minutes, promptly get described flexible printed circuit substrate.
Embodiment 5
Get vinylbenzene 50 grams, butyl acrylate 20 grams, vinyl cyanide 15 grams, allyl group phosphoric acid ethyl phenyl ester 30 grams, vinylformic acid 4 grams, propenoic acid beta-hydroxy base butyl ester 2 grams, Potassium Persulphate 2 grams, glycerine single-hard ester acid ester and tween 80 be totally 6 grams, deionized water 200 grams, reflux is 3 hours in 500 milliliters of four-hole boiling flasks that have agitator, prolong, thermometer, the cooling, filter the multi-component copolymer acrylate emulsion.Add tricresyl phosphate isopropyl benzene ester 5 grams, talcum powder 8 grams mix, and promptly get flame retardant adhesive without halogen in use for flexible printed circuit of the present invention.
The tackiness agent that makes is evenly coated in the one side of the Kapton of 12.5 micron thickness, and preliminary drying is 30 minutes in 110 ± 5 ℃ baking oven, is cooled to room temperature.Superimposed with the electrolytic copper foil of 50 micron thickness, in the composite pressure machine in 130 ℃, 45 kg/cm
2Under the pressure, kept 100 minutes, promptly get described flexible printed circuit substrate.
Embodiment 6
Get vinyl acetate 80 grams, vinyl cyanide 30 grams, methacrylic heptyl heptylate 60 grams, allyl group phosphoric acid ethyltoluene base ester 50 grams, propenoic acid beta-hydroxy base ethyl ester 20 grams, ammonium persulphate 5 grams, sodium laurylsulfonate and Si Ban 60 be totally 10 grams, deionized water 600 grams, and reflux is 9 hours in having the 2000ml four-hole boiling flask of agitator, prolong, thermometer, the cooling, filter the multi-component copolymer acrylate emulsion.Add tricresyl phosphate isopropyl benzene ester 30 grams, talcum powder 30 grams mix, and promptly get flame retardant adhesive without halogen in use for flexible printed circuit of the present invention.
The tackiness agent that makes is evenly coated in the one side of the Kapton of 25 micron thickness, and preliminary drying is 60 minutes in 110 ± 5 ℃ baking oven, is cooled to room temperature.Superimposed with the electrolytic copper foil of 12 micron thickness, in the composite pressure machine in 190 ℃, 55 kg/cm
2Under the pressure, kept 80 minutes, promptly get described flexible printed circuit substrate.
Comparative Examples 1
Get vinyl acetate between to for plastic 40 grams, Octyl methacrylate 30 grams, vinyl cyanide 25 grams, propenoic acid beta-hydroxy base heptyl ester 6 grams, Methacrylamide 2 grams, 2,2 '-2,2'-Azobis(2,4-dimethylvaleronitrile) 5 grams, stearyl vitriolate of tartar and OP-10 be totally 10 grams, deionized water 600 grams, reflux is 6 hours in 1000 milliliters of four-hole boiling flasks that have agitator, prolong, thermometer, the cooling, filter the multi-component copolymer acrylate emulsion.Add magnesium hydroxide 30 grams, mix, promptly get flame retardant adhesive without halogen in use for flexible printed circuit of the present invention.
The tackiness agent that makes is evenly coated in the one side of the Kapton of 12.5 micron thickness, and preliminary drying is 30 minutes in 115 ± 5 ℃ baking oven, is cooled to room temperature.Superimposed with the electrolytic copper foil of 50 micron thickness, in the composite pressure machine in 180 ℃, 55 kg/cm
2Under the pressure, kept 70 minutes, promptly get described flexible printed circuit substrate.
It is as shown in table 1 that multi-component copolymer non-halogen flame-proof acrylic ester gum stick is applied to the performance of the embodiment of flexible polyimide copper clad lamination and Comparative Examples.
Table 1 multi-component copolymer non-halogen flame-proof acrylic ester gum stick is applied to the embodiment of flexible polyimide copper clad lamination and the performance of Comparative Examples
Claims (13)
1, a kind of flexible printed circuit is characterized in that with non-halogen flame-proof acrylic ester gum stick, with following each component be raw material through reacting made, according to the mass fraction, the amount of each raw material is:
100 parts of multicomponent methacrylate comonomers,
5～40 parts of allyl group phosphate ester monomers,
1～10 part of cross-linking modified monomer,
100～500 parts of deionized waters,
1～10 part of reaction initiator,
1～10 part of emulsifying agent,
10～60 parts of phosphorous fillers,
10～50 parts of mineral fillers,
Wherein, described multicomponent methacrylate comonomer is one or more the mixture in alkyl acrylate, alkyl methacrylate, vinylbenzene and vinyl cyanide and the vinyl acetate; Described allyl group phosphate ester monomer is one or more the mixture in allyl group phosphate dialkyl ester, allyl group di(2-ethylhexyl)phosphate aromatic ester and the allyl group alkyl aryl phosphate; Described cross-linking modified monomer is methacrylic acid, vinylformic acid, methacrylic acid β-C
2～C
8Hydroxy ester, propenoic acid beta-C
2～C
8In hydroxy ester, acrylamide, Methacrylamide and the glycidyl acrylate two or more contains the mixture of different crosslinked groups; Described reaction initiator be 2-(tertiary butyl azo) butyronitrile, 2,2 '-2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2 '-one or more mixture in Diisopropyl azodicarboxylate, dilauroyl peroxide, dibenzoyl peroxide, Potassium Persulphate and the ammonium persulphate; Described emulsifying agent is one or more of the positive alkyl sodium sulfate salt of anionic, positive mersolates, glycerine single-hard ester acid ester and alkylaryl sulphonate, with one or more the mixture in the octyl phenol polyoxy vinyl alcohol that contains oxyethane, polysorbate60, tween 80, polysorbas20, class of department 80 and the class of department 65 of non-ionic type; Described phosphorous filler is one or more the mixture in triethyl phosphate, tributyl phosphate, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate biphenyl ester and the tricresyl phosphate isopropyl benzene ester; Described mineral filler is one or more the mixture in silicon-dioxide, aluminum oxide, talcum powder, lime carbonate, magnesiumcarbonate, zinc borate, zinc oxide, potassium titanate, silicon nitride, boron nitride, aluminium hydroxide and the magnesium hydroxide.
2, flexible printed circuit as claimed in claim 1 is characterized in that with non-halogen flame-proof acrylic ester gum stick, with following each component be raw material through reacting made, according to the mass fraction, the amount of each raw material is:
100 parts of multicomponent methacrylate comonomers,
10～30 parts of allyl group phosphate ester monomers,
5～10 parts of cross-linking modified monomers,
150～300 parts of deionized waters,
3～8 parts of reaction initiators,
2～7 parts of emulsifying agents,
20～30 parts of phosphorous fillers,
20～40 parts of mineral fillers.
3, flexible printed circuit as claimed in claim 1 or 2 is characterized in that with non-halogen flame-proof acrylic ester gum stick described multicomponent methacrylate comonomer is methacrylic acid C
1～C
8Alkyl ester and vinyl cyanide.
4, flexible printed circuit as claimed in claim 1 or 2 is characterized in that with non-halogen flame-proof acrylic ester gum stick described allyl group phosphate ester monomer is allyl group di(2-ethylhexyl)phosphate C
1～C
8Alkyl ester.
5, flexible printed circuit as claimed in claim 1 or 2 is characterized in that with non-halogen flame-proof acrylic ester gum stick described cross-linking modified monomer is methacrylic acid and propenoic acid beta-C
2～C
8Hydroxy ester.
6, flexible printed circuit as claimed in claim 1 or 2 is characterized in that with non-halogen flame-proof acrylic ester gum stick, described reaction initiator is 2,2 '-Diisopropyl azodicarboxylate and ammonium persulphate.
7, flexible printed circuit as claimed in claim 1 or 2 is characterized in that with non-halogen flame-proof acrylic ester gum stick, and described emulsifying agent is sodium laurylsulfonate and the octyl phenol polyoxy vinyl alcohol OP-10 that contains 10 moles of ethylene oxide.
8, flexible printed circuit as claimed in claim 1 or 2 is characterized in that with non-halogen flame-proof acrylic ester gum stick described phosphorous filler is a triphenylphosphate.
9, flexible printed circuit as claimed in claim 1 or 2 is characterized in that with non-halogen flame-proof acrylic ester gum stick described mineral filler is silicon-dioxide and magnesium hydroxide.
10, claim 1 or the 2 described flexible printed circuits preparation method of non-halogen flame-proof acrylic ester gum stick is characterized in that preparation process is:
Step 1, the multicomponent methacrylate monomer with selected, allyl group phosphate ester monomer, cross-linking monomer, reaction initiator, emulsifying agent, deionized water add to have in heating, stirring, backflow, the thermometric reactor in described ratio and mix;
Step 2, feeding nitrogen stir, and control reaction temperature was reacted 1～24 hour between 40 ℃～150 ℃, and discharging is filtered in cooling;
Step 3, add phosphorous filler, mineral filler, mix, keeping the solid content mass percent is 15%～40% promptly to get described tackiness agent.
11, flexible printed circuit as claimed in claim 10 is characterized in that described temperature of reaction between 60 ℃～120 ℃ with the preparation method of non-halogen flame-proof acrylic ester gum stick, reacts 3～8 hours.
12, claim 1 or 2 application of described tackiness agent in flexible printed circuit is characterized in that described tackiness agent is evenly coated in the one side of polyimide or polyester film, and thick 10～40 microns of glue is with Copper Foil or the compound flexible printed circuit base material that makes of aluminium foil.
13, the application of tackiness agent as claimed in claim 12 in flexible printed circuit, it is characterized in that Copper Foil or aluminium foil and the insulation film compound temperature of tackiness agent is arranged is that 120 ℃～200 ℃, pressure are 20～60 kg/cm
2, the time is 20～180 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101244564A CN100425668C (en) | 2006-09-06 | 2006-09-06 | Flame retardant adhesive without halogen in use for flexible printed circuit |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101244564A CN100425668C (en) | 2006-09-06 | 2006-09-06 | Flame retardant adhesive without halogen in use for flexible printed circuit |
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| CN1916101A CN1916101A (en) | 2007-02-21 |
| CN100425668C true CN100425668C (en) | 2008-10-15 |
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| CN101851378A (en) * | 2010-03-05 | 2010-10-06 | 上海锦湖日丽塑料有限公司 | Extrusion grade ASA resin with easy processing and high apparent property and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09296090A (en) * | 1996-04-30 | 1997-11-18 | Mitsubishi Rayon Co Ltd | Flame-retardant methacrylic resin composition |
| JPH09302191A (en) * | 1996-05-14 | 1997-11-25 | Mitsubishi Rayon Co Ltd | Methacrylic resin composition |
| CN1282360A (en) * | 1997-11-20 | 2001-01-31 | 阿什兰公司 | Pressure-sensitive flame retardant adhesive |
-
2006
- 2006-09-06 CN CNB2006101244564A patent/CN100425668C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09296090A (en) * | 1996-04-30 | 1997-11-18 | Mitsubishi Rayon Co Ltd | Flame-retardant methacrylic resin composition |
| JPH09302191A (en) * | 1996-05-14 | 1997-11-25 | Mitsubishi Rayon Co Ltd | Methacrylic resin composition |
| CN1282360A (en) * | 1997-11-20 | 2001-01-31 | 阿什兰公司 | Pressure-sensitive flame retardant adhesive |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851378A (en) * | 2010-03-05 | 2010-10-06 | 上海锦湖日丽塑料有限公司 | Extrusion grade ASA resin with easy processing and high apparent property and preparation method thereof |
| CN101851378B (en) * | 2010-03-05 | 2012-10-03 | 上海锦湖日丽塑料有限公司 | Extrusion grade ASA resin with easy processing and high apparent property and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1916101A (en) | 2007-02-21 |
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