CA2187316C - High temperature resistant antistatic pressure-sensitive adhesive tape - Google Patents
High temperature resistant antistatic pressure-sensitive adhesive tape Download PDFInfo
- Publication number
- CA2187316C CA2187316C CA002187316A CA2187316A CA2187316C CA 2187316 C CA2187316 C CA 2187316C CA 002187316 A CA002187316 A CA 002187316A CA 2187316 A CA2187316 A CA 2187316A CA 2187316 C CA2187316 C CA 2187316C
- Authority
- CA
- Canada
- Prior art keywords
- acrylate
- vinyl
- adhesive tape
- sensitive adhesive
- heat
- 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.)
- Expired - Fee Related
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 29
- 239000000853 adhesive Substances 0.000 claims abstract description 54
- 230000001070 adhesive effect Effects 0.000 claims abstract description 54
- 239000011859 microparticle Substances 0.000 claims abstract description 31
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 25
- 229920005601 base polymer Polymers 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 19
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000679 solder Inorganic materials 0.000 claims abstract description 17
- 239000002390 adhesive tape Substances 0.000 claims abstract description 15
- 239000005011 phenolic resin Substances 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000004020 conductor Substances 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 7
- 238000007654 immersion Methods 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 47
- -1 polyethylene Polymers 0.000 claims description 43
- 239000002987 primer (paints) Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 25
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229920001567 vinyl ester resin Polymers 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229920001748 polybutylene Polymers 0.000 claims description 9
- 229920001721 polyimide Polymers 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000004642 Polyimide Substances 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 8
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 claims description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 5
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- 150000003926 acrylamides Chemical class 0.000 claims description 4
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 4
- 229920005549 butyl rubber Polymers 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 229920001195 polyisoprene Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 claims description 3
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 claims description 3
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 claims description 3
- QBDADGJLZNIRFQ-UHFFFAOYSA-N ethenyl octanoate Chemical compound CCCCCCCC(=O)OC=C QBDADGJLZNIRFQ-UHFFFAOYSA-N 0.000 claims description 3
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 claims description 3
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011152 fibreglass Substances 0.000 claims description 3
- 150000002466 imines Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 3
- YCJYNBLLJHFIIW-MBABXGOBSA-N validoxylamine A Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)C[C@@H]1N[C@@H]1[C@H](O)[C@@H](O)[C@H](O)C(CO)=C1 YCJYNBLLJHFIIW-MBABXGOBSA-N 0.000 claims description 3
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 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 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 229940048053 acrylate Drugs 0.000 description 22
- 239000003995 emulsifying agent Substances 0.000 description 20
- 239000002245 particle Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 238000012546 transfer Methods 0.000 description 14
- 239000012071 phase Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000007900 aqueous suspension Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 230000000873 masking effect Effects 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000005476 soldering Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 239000007762 w/o emulsion Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 229940114077 acrylic acid Drugs 0.000 description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000011800 void material Substances 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000000712 assembly Effects 0.000 description 3
- 238000000429 assembly Methods 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229960004592 isopropanol Drugs 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000013464 silicone adhesive Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical class CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 2
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 2
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007764 o/w emulsion Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical class [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- GPMCZKILFBRNNY-UHFFFAOYSA-N 2,3-bis(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=C(O)C=CC(O)=C1C(C)(C)CC GPMCZKILFBRNNY-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- NCTBYWFEJFTVEL-UHFFFAOYSA-N 2-methylbutyl prop-2-enoate Chemical compound CCC(C)COC(=O)C=C NCTBYWFEJFTVEL-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- BVDBXCXQMHBGQM-UHFFFAOYSA-N 4-methylpentan-2-yl prop-2-enoate Chemical compound CC(C)CC(C)OC(=O)C=C BVDBXCXQMHBGQM-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- LIFHMKCDDVTICL-UHFFFAOYSA-N 6-(chloromethyl)phenanthridine Chemical compound C1=CC=C2C(CCl)=NC3=CC=CC=C3C2=C1 LIFHMKCDDVTICL-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229910017974 NH40H Inorganic materials 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- 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 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002998 adhesive polymer Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OPVLOHUACNWTQT-UHFFFAOYSA-N azane;2-dodecoxyethyl hydrogen sulfate Chemical compound N.CCCCCCCCCCCCOCCOS(O)(=O)=O OPVLOHUACNWTQT-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000007760 metering rod coating Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- QGMRQYFBGABWDR-UHFFFAOYSA-N sodium;5-ethyl-5-pentan-2-yl-1,3-diazinane-2,4,6-trione Chemical compound [Na+].CCCC(C)C1(CC)C(=O)NC(=O)NC1=O QGMRQYFBGABWDR-UHFFFAOYSA-N 0.000 description 1
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- MXODCLTZTIFYDV-UHFFFAOYSA-L zinc;1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Zn+2].C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C([O-])=O.C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C([O-])=O MXODCLTZTIFYDV-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
- H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/01—Tools for processing; Objects used during processing
- H05K2203/0191—Using tape or non-metallic foil in a process, e.g. during filling of a hole with conductive paste
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/125—Inorganic compounds, e.g. silver salt
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3452—Solder masks
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
There is provided a heat-resistant anti-static pressure-sensitive adhesive tape comprising a substrate having opposing surfaces, at least one of said surfaces bearing thereon an acrylic microparticulate adhesive wherein the microparticles have an average diameter of 1 to 250 micrometers, wherein the microparticles have a surface bearing thereon an ionic conductive material formed from a polymer electrolyte base polymer and at least one ionic salt selected from the group consisting of salts of alkali metals and salts of alkaline earth metals, said adhesive being bonded to said substrate by means of a primer, said primer comprising at least one phenolic resin and at least one rubbery compound, said adhesive tape being capable of surviving immersion in molten solder at 260.degree.C for at least 5 seconds.
Description
WO 95130720 218 7 316 pCTlU895103°81 HIGH TEMPERATURE RESISTANT ANTISTATIC
PRESSURE-SENSITIVE ADHESIVE TAPE
Background of the Invention Field of the Invention The invention relates to pressure-sensitive adhesive ' tape constructions which are useful for masking printed circuit boards (PCBs) at the high temperatures associated with wave soldering operations. These adhesive tapes, which comprise ionically conductive polymeric microparticulate adhesive formulations, provide tapes extremely resistant to tribocharging, thereby protecting electronic components from static charge buildup. In addition, the adhesive masking tape, upon removal from a PCB, does not contaminate the surface of the board with adhesive residue.
Description of the Art The process of wave soldering is commonly used for permanently attaching electronic components to printed circuit boards. Various methods are used to mask or cover areas of the board during the wave soldering attachment process where solder is not desired. It is known, for example, to achieve such masking by use of self-adhesive tapes based on high-temperature-resistant polyimide film coated with a silicone-based adhesive.
However, the removal of such tapes from the surface of electronic assemblies causes tribocharging accompanied by static charges which can damage sensitive electronic components and cause contamination of the printed circuits by silicone.
Electrically conductive tapes are also useful for -the masking purpose. Electrically conductive tapes do ' not tribocharge as readily as those made from insulating materials such as silicones. The use of conductive WO 95130720 218 7 31 b PCT/US95/03381 _2_ tapes, in assembly operat-ions, therefore, will reduce the failure rate of electronic components.
Several different types of conductive tape are=known for use. at ambient temperatures. United States patents 3,104,985, 3,832,598 and 4,749,612 describe adhesive tapes with a coating of.carbon black in a binder which is taught to dissipate electrostatic charges. Various patents also disclose multiple layer tape structures wherein one-of the layers, usually a buried layer, is electrically conductive.
For example, Japanese Patent Publication J 63012681-A discloses a tape with an intermediate, antistatic polymer layer situated between a polyolefin support and a rubber adhesive layer.
European Patent Publication EP- 0422919-A2 discloses a tape having a layer of conductive particles or conductive foil surrounded by binder, situated between a polymer film support and a silicone adhesive. The use of a high temperature film support, po-lyimide, combined with silicone binder and adhesive, is stated to yield a tape which will perform well as a-wave solder masking tape at temperatures unsuitable for earlier antistatic tapes, i.e., this tape will survive-in a wave solder bath for up to 5 seconds at 250°C.
Antistatic or conductive tapes which rely on the use of conductive particles require high loading of these particles.for sufficient electrostatic charge-neutralization. The effect of the conductive particles must be active at the surface of an otherwise-insulative adhesive for static free masking of electronic assemblies. Charge transfer to the underlying layer of conductive particles requires a conductive pathway through the adhesive. However, high particulate loading often leads to loss of adhesion and undesirable transfer of contaminating material. This problem must be balanced R'O 95130720 PCT/US95/03381 against the use of additional polymeric binder which may electrically insulate adjacent conductive particles and thus cause increased tribocharging while reducing transfer-.
The need for balance between particle loading and polymeric binder could be avoided with an inherently conductive adhesive layer. However, there is no known disclosure of a wave solder masking tape using an inherently conductive adhesive in direct contact with the printed circuit board. Whether conductive in nature or not, most non-silicone adhesives will not survive the wave soldering process, and are thus not useful for such an application.
The current inventors have discovered an inherently conductive adhesive useful at the high temperatures required by wave solder baths. When coated onto a highly temperature resistant material bearing a specific primer thereon, a tape construction is provided which is useful for wave soldering applications without the problems of previously disclosed wave solder masking tapes.
Adhesive tapes of the invention comprise sonically charged acrylic microparticulate adhesives. Polymeric microparticles having polymer-electrolytes on the surface of each polymer particle provide conductive particles which are useful as antistatic adhesive compositions.
Surprisingly such adhesives exhibit high temperature resistance when placed in a wave solder bath.
Particulate adhesives are also known in the art, and have been coated on a variety of substrates and used primarily in applications requiring a low level of adhesion, e.g., repositionability. Such spheres and their use in aerosol adhesive systems having repositionable properties are disclosed in U.S. Pat. No.
3,691,140 (Silver). These microparticles are prepared by aqueous suspension polymerization of alkyl acrylate WO 95!30720 218 7 315 P~'f1~1S95103381 -4- .
monomers and ionic comonomer, e.g:, sodium methacrylate, in the presence of an emulsifier. The use of-a water-soluble, substantially oil-insoluble ionic comonome~-is r critical to preventing coagulation or agglomeration of the microparticles. However, particulate adhesives disclosed in the prior art have all-been useful as repositionable adhesives for such applications as Post-It'M brand notes, and other removable items.
Pressure-sensitive tapes made with this type of adhesive are likely to be considered unsuitable for use as antistatic tapes due to their lack of conductivity, and ease ofremoval. Further; acrylic adhesives are typically not considered to be heat resistant in nature.
Adhesive tapes of the invention provide antistatic tapes which are extremely effective in dissipating electrostatic charge and may be used in sensitive applications without worry about adhesive transfer.
Summary of the Invention The invention provides a high-temperature resistant, antistatic, pressure-sensitive adhesive tape comprising a polymeric film support bearing a primer which causes a non-tribocharging, microparticulate adhesive to strongly adhere to the backing. This tape has the capacity to survive immersion in molten solder, at-elevated temperature, essentially unchanged for periods of up to 5 seconds, preferably up to 20 seconds.
More specifically, the-invention provides a heat-resistant anti-static pressure-sensitive adhesive tape comprising a substrate having opposing surfaces, at least one surface bearing thereon, a microparticulate adhesive having an average diameter of atleast 1 micrometer,-wherein the microparticles have a surface bearing thereon an ionic conductive material formed from a polymer b electrolyte base polymer, and at least one ionic salt selected from the group consisting of salts of alkali metals and salts of alkaline earth metals, said adhesive being adhered to said substrate by means of a primer composition, said primer comprising at least one phenolic resin and at least one rubbery compound, said adhesive tape surviving in a wave-solder bath for at least 5 seconds.
According to one aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape comprising a substrate having opposing surfaces, at least one of said surfaces bearing thereon an acrylic microparticulate adhesive wherein the microparticles have an average diameter of 1 to 250 micrometers, wherein the microparticles have a surface bearing thereon an ionic conductive material formed from a polymer electrolyte base polymer and at least one ionic salt selected from the group consisting of salts of alkali metals and salts of alkaline earth metals, said adhesive being bonded to said substrate by means of a primer, said primer comprising at least one phenolic resin and at least one rubbery compound, said adhesive tape being capable of surviving immersion in molten solder at 260°C for at least 5 seconds.
According to another aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein said at least one phenolic resin is a phenol-formaldehyde resin.
According to still another aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein -5a-said primer coating comprises at least one rubbery compound selected from the group consisting of a butyl rubber, an acrylonitrile-butadiene copolymer, an acrylonitrile-butadiene-styrene copolymer, a styrene-butadiene-styrene copolymer, a styrene-ethylene butylene-styrene copolymer, polychloroprene, polybutadiene, polyisoprene, and a styrene-isoprene-styrene copolymer.
According to yet another aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein said primer coating comprises a mixture of acrylonitrile-butadiene-styrene copolymer and polychloroprene.
According to a further aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein said microparticulate adhesive comprises a polymer of monomers comprising: a) at least 70 parts of at least one alkyl (meth)acrylate or vinyl ester, b) correspondingly, up to 30 parts of at least one polar monomer, to make 100 parts monomer, and wherein said ionic conductive material comprises a polymer electrolyte formed from a polymer electrolyte base polymer selected from the group consisting of polyethylene oxide, polyphenylene oxide, polyphenylene sulfide, polyethylene sulfide, polyethyleneimine, polypropylene oxide, polybutylene oxide, polybutylene sulfide, and polybutylene imine, said polymer electrolyte base polymer is added in an amount of from 0.1 part to 10 parts per 100 parts monomer.
According to yet a further aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein said ionic conductive material comprises from 0.01 moles to -5b-moles of at least one salt of an alkali metal or alkaline earth metal per mole of the polymer electrolyte base polymer.
According to still a further aspect of the present 5 invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein said salt is selected from the group consisting of LiCl, LiN03, LiCF3S03, LiS09, LiOH, KOH, NaSCN, NaI, BaS03CF3, and NH40H .
10 According to another aspect of the present invention, there is provided a heat-resistant anti-static pressure sensitive adhesive tape described herein, wherein the at least one alkyl (meth)acrylate comprises one of more component selected from the group consisting of isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isoamyl (meth)acrylate, isodecyl (meth)acrylate, and butyl (meth)acrylate, the at least one vinyl ester comprises one or more component selected from the group consisting of vinyl 2-ethylhexanoate, vinyl caproate, vinyl laurate, vinyl pelargonate, vinyl hexanoate, vinyl propionate, vinyl decanoate, and vinyl octanoate, and the at least one polar monomer comprises one or more component selected from the group consisting of N-vinyl-2-pyrrolidone, N-vinyl caprolactam, acrylonitrile, vinyl acrylate, diallyl phthalate, acrylic acid, methacrylic acid, itaconic acid, an hydroxyalkyl acrylate, a cyanoalkyl acrylate, an acrylamide, and a substituted acrylamide.
According to yet another aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein said substrate is selected from the group consisting of polyimide, polyphenylene sulfide, heat-treated non-woven -5c-material, fiberglass, metallized polymeric film, ceramic sheet material, and metal foil.
According to yet another aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein said substrate is polyimide.
Preferably, the heat-resistant anti-static pressure-sensitive adhesive tape of the invention comprises an adhesive polymer of monomers comprising:
a) at least 70 parts of at least one alkyl (meth)acrylate or vinyl ester, b) correspondingly, up to 30 parts of at least one polar monomer, to make 100 parts monomer, and wherein said ionic conductive material comprises a polymer electrolyte formed from a polymer electrolyte base polymer, said polymer electrolyte base polymer added in an amount of from 0.1 part to 10 parts, said adhesive being adhered to said substrate by means of a primer composition, said primer comprising at least one phenolic formaldehyde resin and at least one rubbery compound selected from the group consisting of butyl rubbers, acrylonitrile-butadiene, acrylonitrile-butadiene-styrene copolymers, styrene-butadiene-styrene, styrene-ethylene butylene-styrene, polychloroprene, polybutadiene, polyisoprene, styrene-isoprene-styrene, and mixtures thereof, said adhesive tape surviving in a wave-solder bath for at least 10 seconds.
As used herein, these terms have the following meanings.
1. The term "polymer electrolyte base polymer" means a polymer which is capable of forming a polymeric species containing electron donating atoms which may be associated with acceptor atoms during formation of the microparticle.
PRESSURE-SENSITIVE ADHESIVE TAPE
Background of the Invention Field of the Invention The invention relates to pressure-sensitive adhesive ' tape constructions which are useful for masking printed circuit boards (PCBs) at the high temperatures associated with wave soldering operations. These adhesive tapes, which comprise ionically conductive polymeric microparticulate adhesive formulations, provide tapes extremely resistant to tribocharging, thereby protecting electronic components from static charge buildup. In addition, the adhesive masking tape, upon removal from a PCB, does not contaminate the surface of the board with adhesive residue.
Description of the Art The process of wave soldering is commonly used for permanently attaching electronic components to printed circuit boards. Various methods are used to mask or cover areas of the board during the wave soldering attachment process where solder is not desired. It is known, for example, to achieve such masking by use of self-adhesive tapes based on high-temperature-resistant polyimide film coated with a silicone-based adhesive.
However, the removal of such tapes from the surface of electronic assemblies causes tribocharging accompanied by static charges which can damage sensitive electronic components and cause contamination of the printed circuits by silicone.
Electrically conductive tapes are also useful for -the masking purpose. Electrically conductive tapes do ' not tribocharge as readily as those made from insulating materials such as silicones. The use of conductive WO 95130720 218 7 31 b PCT/US95/03381 _2_ tapes, in assembly operat-ions, therefore, will reduce the failure rate of electronic components.
Several different types of conductive tape are=known for use. at ambient temperatures. United States patents 3,104,985, 3,832,598 and 4,749,612 describe adhesive tapes with a coating of.carbon black in a binder which is taught to dissipate electrostatic charges. Various patents also disclose multiple layer tape structures wherein one-of the layers, usually a buried layer, is electrically conductive.
For example, Japanese Patent Publication J 63012681-A discloses a tape with an intermediate, antistatic polymer layer situated between a polyolefin support and a rubber adhesive layer.
European Patent Publication EP- 0422919-A2 discloses a tape having a layer of conductive particles or conductive foil surrounded by binder, situated between a polymer film support and a silicone adhesive. The use of a high temperature film support, po-lyimide, combined with silicone binder and adhesive, is stated to yield a tape which will perform well as a-wave solder masking tape at temperatures unsuitable for earlier antistatic tapes, i.e., this tape will survive-in a wave solder bath for up to 5 seconds at 250°C.
Antistatic or conductive tapes which rely on the use of conductive particles require high loading of these particles.for sufficient electrostatic charge-neutralization. The effect of the conductive particles must be active at the surface of an otherwise-insulative adhesive for static free masking of electronic assemblies. Charge transfer to the underlying layer of conductive particles requires a conductive pathway through the adhesive. However, high particulate loading often leads to loss of adhesion and undesirable transfer of contaminating material. This problem must be balanced R'O 95130720 PCT/US95/03381 against the use of additional polymeric binder which may electrically insulate adjacent conductive particles and thus cause increased tribocharging while reducing transfer-.
The need for balance between particle loading and polymeric binder could be avoided with an inherently conductive adhesive layer. However, there is no known disclosure of a wave solder masking tape using an inherently conductive adhesive in direct contact with the printed circuit board. Whether conductive in nature or not, most non-silicone adhesives will not survive the wave soldering process, and are thus not useful for such an application.
The current inventors have discovered an inherently conductive adhesive useful at the high temperatures required by wave solder baths. When coated onto a highly temperature resistant material bearing a specific primer thereon, a tape construction is provided which is useful for wave soldering applications without the problems of previously disclosed wave solder masking tapes.
Adhesive tapes of the invention comprise sonically charged acrylic microparticulate adhesives. Polymeric microparticles having polymer-electrolytes on the surface of each polymer particle provide conductive particles which are useful as antistatic adhesive compositions.
Surprisingly such adhesives exhibit high temperature resistance when placed in a wave solder bath.
Particulate adhesives are also known in the art, and have been coated on a variety of substrates and used primarily in applications requiring a low level of adhesion, e.g., repositionability. Such spheres and their use in aerosol adhesive systems having repositionable properties are disclosed in U.S. Pat. No.
3,691,140 (Silver). These microparticles are prepared by aqueous suspension polymerization of alkyl acrylate WO 95!30720 218 7 315 P~'f1~1S95103381 -4- .
monomers and ionic comonomer, e.g:, sodium methacrylate, in the presence of an emulsifier. The use of-a water-soluble, substantially oil-insoluble ionic comonome~-is r critical to preventing coagulation or agglomeration of the microparticles. However, particulate adhesives disclosed in the prior art have all-been useful as repositionable adhesives for such applications as Post-It'M brand notes, and other removable items.
Pressure-sensitive tapes made with this type of adhesive are likely to be considered unsuitable for use as antistatic tapes due to their lack of conductivity, and ease ofremoval. Further; acrylic adhesives are typically not considered to be heat resistant in nature.
Adhesive tapes of the invention provide antistatic tapes which are extremely effective in dissipating electrostatic charge and may be used in sensitive applications without worry about adhesive transfer.
Summary of the Invention The invention provides a high-temperature resistant, antistatic, pressure-sensitive adhesive tape comprising a polymeric film support bearing a primer which causes a non-tribocharging, microparticulate adhesive to strongly adhere to the backing. This tape has the capacity to survive immersion in molten solder, at-elevated temperature, essentially unchanged for periods of up to 5 seconds, preferably up to 20 seconds.
More specifically, the-invention provides a heat-resistant anti-static pressure-sensitive adhesive tape comprising a substrate having opposing surfaces, at least one surface bearing thereon, a microparticulate adhesive having an average diameter of atleast 1 micrometer,-wherein the microparticles have a surface bearing thereon an ionic conductive material formed from a polymer b electrolyte base polymer, and at least one ionic salt selected from the group consisting of salts of alkali metals and salts of alkaline earth metals, said adhesive being adhered to said substrate by means of a primer composition, said primer comprising at least one phenolic resin and at least one rubbery compound, said adhesive tape surviving in a wave-solder bath for at least 5 seconds.
According to one aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape comprising a substrate having opposing surfaces, at least one of said surfaces bearing thereon an acrylic microparticulate adhesive wherein the microparticles have an average diameter of 1 to 250 micrometers, wherein the microparticles have a surface bearing thereon an ionic conductive material formed from a polymer electrolyte base polymer and at least one ionic salt selected from the group consisting of salts of alkali metals and salts of alkaline earth metals, said adhesive being bonded to said substrate by means of a primer, said primer comprising at least one phenolic resin and at least one rubbery compound, said adhesive tape being capable of surviving immersion in molten solder at 260°C for at least 5 seconds.
According to another aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein said at least one phenolic resin is a phenol-formaldehyde resin.
According to still another aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein -5a-said primer coating comprises at least one rubbery compound selected from the group consisting of a butyl rubber, an acrylonitrile-butadiene copolymer, an acrylonitrile-butadiene-styrene copolymer, a styrene-butadiene-styrene copolymer, a styrene-ethylene butylene-styrene copolymer, polychloroprene, polybutadiene, polyisoprene, and a styrene-isoprene-styrene copolymer.
According to yet another aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein said primer coating comprises a mixture of acrylonitrile-butadiene-styrene copolymer and polychloroprene.
According to a further aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein said microparticulate adhesive comprises a polymer of monomers comprising: a) at least 70 parts of at least one alkyl (meth)acrylate or vinyl ester, b) correspondingly, up to 30 parts of at least one polar monomer, to make 100 parts monomer, and wherein said ionic conductive material comprises a polymer electrolyte formed from a polymer electrolyte base polymer selected from the group consisting of polyethylene oxide, polyphenylene oxide, polyphenylene sulfide, polyethylene sulfide, polyethyleneimine, polypropylene oxide, polybutylene oxide, polybutylene sulfide, and polybutylene imine, said polymer electrolyte base polymer is added in an amount of from 0.1 part to 10 parts per 100 parts monomer.
According to yet a further aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein said ionic conductive material comprises from 0.01 moles to -5b-moles of at least one salt of an alkali metal or alkaline earth metal per mole of the polymer electrolyte base polymer.
According to still a further aspect of the present 5 invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein said salt is selected from the group consisting of LiCl, LiN03, LiCF3S03, LiS09, LiOH, KOH, NaSCN, NaI, BaS03CF3, and NH40H .
10 According to another aspect of the present invention, there is provided a heat-resistant anti-static pressure sensitive adhesive tape described herein, wherein the at least one alkyl (meth)acrylate comprises one of more component selected from the group consisting of isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isoamyl (meth)acrylate, isodecyl (meth)acrylate, and butyl (meth)acrylate, the at least one vinyl ester comprises one or more component selected from the group consisting of vinyl 2-ethylhexanoate, vinyl caproate, vinyl laurate, vinyl pelargonate, vinyl hexanoate, vinyl propionate, vinyl decanoate, and vinyl octanoate, and the at least one polar monomer comprises one or more component selected from the group consisting of N-vinyl-2-pyrrolidone, N-vinyl caprolactam, acrylonitrile, vinyl acrylate, diallyl phthalate, acrylic acid, methacrylic acid, itaconic acid, an hydroxyalkyl acrylate, a cyanoalkyl acrylate, an acrylamide, and a substituted acrylamide.
According to yet another aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein said substrate is selected from the group consisting of polyimide, polyphenylene sulfide, heat-treated non-woven -5c-material, fiberglass, metallized polymeric film, ceramic sheet material, and metal foil.
According to yet another aspect of the present invention, there is provided a heat-resistant anti-static pressure-sensitive adhesive tape described herein, wherein said substrate is polyimide.
Preferably, the heat-resistant anti-static pressure-sensitive adhesive tape of the invention comprises an adhesive polymer of monomers comprising:
a) at least 70 parts of at least one alkyl (meth)acrylate or vinyl ester, b) correspondingly, up to 30 parts of at least one polar monomer, to make 100 parts monomer, and wherein said ionic conductive material comprises a polymer electrolyte formed from a polymer electrolyte base polymer, said polymer electrolyte base polymer added in an amount of from 0.1 part to 10 parts, said adhesive being adhered to said substrate by means of a primer composition, said primer comprising at least one phenolic formaldehyde resin and at least one rubbery compound selected from the group consisting of butyl rubbers, acrylonitrile-butadiene, acrylonitrile-butadiene-styrene copolymers, styrene-butadiene-styrene, styrene-ethylene butylene-styrene, polychloroprene, polybutadiene, polyisoprene, styrene-isoprene-styrene, and mixtures thereof, said adhesive tape surviving in a wave-solder bath for at least 10 seconds.
As used herein, these terms have the following meanings.
1. The term "polymer electrolyte base polymer" means a polymer which is capable of forming a polymeric species containing electron donating atoms which may be associated with acceptor atoms during formation of the microparticle.
2. The term "polymer electrolyte functional unit"
means the group containing the electron donating species.
The term "microparticle" means a particle having a diameter of from 1 micrometer to 250 micrometers.
4- The term "tribocharging" means electrostatic charge generation associated with friction or separation between separable surfaces.
5. The term "droplet" means the liquid stage of the microparticles prior to the completion of polymerization.
6. The term "cavity" means a space within the walls of a droplet or microparticle when still in the suspension or dispersion medium prior to drying, and thus containing whatever medium was used.
7. The term "void" means an empty space completely within the walls of a polymerized microparticle.
g_ The term "hollow"means containing at least one void or cavity.
g. The term "solid" means voids or cavity-free.
10. The term alkyl (meth)acrylate means an alkyl acrylate or alkyl methacrylate.
11. The term "modified surface" means a surface which has been subjected to a priming, coating or treatment such as chemical or radiation treatment such that the original properties of the surface have been changed.
As used herein, all parts, percents, and ratios are by weight, unless specifically stated otherwise.
Detailed Description of the Invention Alkyl acrylate or methacrylate monomers useful in preparing the microparticles and conductive pressure-sensitive adhesives for use in tapes of this invention are those monofunctional unsaturated acrylate or methacrylic esters of non-tertiary alkyl alcohols, the alkyl groups of which have from 4 to about 14 carbon atoms. Such acrylates.are oleophilic, water emulsifiable, have limited water solubility, and as homopolymers, generally have glass transition temperatures below about -20°C. Included within this class of monomers are, for example, isooctyl acrylate, 4-methyl-2-pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, sec-butyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isodecyl methacrylate, isononyl acrylate, isodecyl acrylate, and the like, singly or in mixtures.
Preferred acrylates include isooctyl acrylate, isononyl acrylate, isoamyl acrylate, isodecyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, sec-butyl acrylate, and mixtures thereof. Acrylate or methacrylate or other vinyl monomers which, as homopolymers, have glass transition temperatures higher than about -20°C, e.g., tert-butyl acrylate, vinyl acetate, and the like, may be utilized in conjunction with one or more of the acrylate or methacrylate monomers provided that the glass transition temperature of the resultant polymer is below about -20°C. When methacrylate monomer is the sole alkyl acrylate utilized, a crosslinking agent, infra, must be included.
Useful vinyl ester monomers are those which form homopolymers having glass transition temperatures below about 10°C. Such esters comprise 2 to 14 carbon atoms, and includes such monomers as vinyl 2-ethylhexanoate, WO 95/30720 ? ~ g 7 3 ~ 6 PCTIUS95103381 -g-vinyl caprate, vinyl laurate,vinyl pelargonate, vinyl hexanoate, vinyl propionate, vinyl decanoate, vinyl octanoate, and the like.
r Useful polar monomers include moderately polar monomers such as N-vinyl-2-pyrrolidone, N-vinyl a caprolactam, acrylonitrile, vinyl acrylate, ahd diallyl .
phthalate, as well as strongly polar monomers such as acrylic--acid, methacrylic acid, itaconic-acid, hydroxyalkyl acrylates, cyanoalkyl acrylates, acrylamides, substituted acrylamides. When more than one polar monomer is used, mixtures may include monomers-having similar or unlike polarities, e.g., one moderately polar and one strongly polar monomer or two monomers from-one group.
The conductive microparticles and the pressure-sensitive adhesives made therefrom comprise at least 70 parts by weight of at least one alkyl (meth)acrylate ester or vinyl ester and correspondingly, up to 30 parts by weight of one or more polar monomers.
Polymer electrolyte base polymers suitable for-use include polyethylene oxide, polyphenylene oxide, polyphenylene sulfide, polyethylene sulfide, polyethyleneimine, polypropylene oxide, polybutylene oxide, polybutylene sulfide, polybutylene imine, and the like. Polyethylene oxide is preferred. Useful amounts of the polymer electrolyte base polymer in microparticles of the invention range from 0.1 part to 10 parts, preferably from 1 part to 5 parts, based on LDO parts monomer weight.
The conductive properties of. the polymeric microparticles may be further enhanced by the addition of ionic salts to adhesive compositions which contain the microparticles. It is believed that the ionic salts become associated with the electron donatinggroups present in the amorphous polymer domains.
WO 95130720 2 ~ ~ 7 3 i ~ PCTlUS95103381 _9_ Salts used for this purpose include salts of alkali metals, and alkaline earth metals, including but not limited to, NaI, NaSCN, BaCF3Sos, NaBr, NaC109, LiCl, LiN03, L1CF3SO3, LiS04, LiOH and KOH. Lithium salts are preferred for the present invention, especially lithium nitrate.
Microparticles may v~e prepared by various emulsification processes, which are varied depending on whether hollow or solid microparticles are desired.
Aqueous suspensions of hollow microparticles may be prepared by a "two-step" emulsification process which first involves forming a water-in-oil emulsion of an aqueous solution of polax- monomers) in oil phase monomer,--i.e., at least cne (meth)acrylate or vinyl ester monomer, with a polymer electrolyte base polymer, using an emulsifier having a lcw hydrophilic-lipophilic balance (HLB) value. Suitable emulsifiers are those having an HLB value below about 7, prefer<:bly in the range of about 2 to about 7. Examples cf-such emulsifiers include sorbitan monooleate, sorbitan trioleate, and ethoxylated oleyl alcohol such as Brij'M 93, available from Atlas Chemical Industries, Inc.
J
WO 95!30720 2 J g ~ 3 ~ a PCTIUS95103381 Thus, in this first step, oil phase monomer(s), polymer electrolyte base polymer, emulsifier, a free-radical initiator, and, optionally, a crosslinking r monomer or monomers as defined below are-combined, and an aqueous solution of all or a-portion of the polar monomers) is agitated and poured into the oil phase mixture to form a water-in-oil emulsion. The polymer electrolyte base polymer may be added to either the-oil -phase or the water-phase. A thickening agent, e.g.~-methyl cellulose may also be included in theaqueous phase of the water-in-oil emulsion. In the s-econd step, a water-in-oil-in-water emulsion is formed by dispersing the water-in-oil emulsion of_the first step into an aqueous phasecontaining an emulsifier-having-an HLB
value above about 6. The aqueous phase may also contain any portion of -the polar monomers) which-was not added in step-one. Examples of such-emulsifiers include ethoxylated sorbitan monooleate, ethoxylated-lauryl alcohol, and alkyl sulfates. In both steps, when an emulsifier is-utilized, its concentration should be-greater than its critical-micelle-concentration, which is herein defined as the minimum concentration of emulsifier necessary for the formation of micelles, i.e.,sub-microscopic aggregations of emulsifier molecules.
Critical micelle concentration is slightly different for each emulsifier; usable concentrations ranging from 1.0 x 10-' to about 3.0 moles/liter. Additional detail concerning the preparation of water-in-oil-in-water,-emulsions, i.e., multiple emulsions, may be found in various literature references, e.g., Surfactant Systems:
Their Chemistry, Pharmacy, & Biology, (D. Attwood and A.
T. Florence, Chapman & Hall-Ztd, New York City, 1983).
The final process step of this method involves-the application of heat or radiation to initiate polymerization of the monomers. Useful initiators are WO 95130720 218 7 316 p~/pS95/0338I
those which are normally suitable for free radical polymerization of acrylate or vinyl ester monomers and which are oil-soluble and of-very low solubility in water. However, when the polar monomer is N-vinyl pyrrolidone, the use of benzoyl peroxide as the initiator is recommended.
Examples of such initiators include azo compounds, hydropex-oxides, peroxides, and the like, and photoinitiators such as benzophenone, benzoin ethyl ether, and 2,2-dimethoxy-2-phenyl acetophenone.
Use of a water-soluble polymerization initiator causes formation of substantial amounts of-latex. The extremely small particle size of latex particles renders any significant formation of latex undesirable. The initiator is generally used in an amount ranging from 0.01 percent up to 10 percent by weight of the total polymerizable composition, preferably up to 5 percent.
Aqueous suspensions of hollow conductive microparticles may also by prepared by a "one-step"
emulsification process. comprising aqueous suspension polymerization of at least one alkyl (meth)acrylate ester monomer or vinyl ester monomer and at least one polar monomer and a polymer electrolyte base polymer in the presence of at least one emulsifier capable of producing a water-in-oil emulsion inside the droplets which is substantially stable during emulsification and polymerization.- As in the two-step emulsification process, the emulsifier is utilized in concentrations greater than its critical micelle concentration. In _ 30 general, high HLB emulsifiers are required, i.e., emulsifiers having an HLB value of at least about 25, will produce stable cavity-containing droplets during the polymerization, and are-suitable for use in this one-step process. Examples of such emulsifiers include alkylarylether sulfates such as sodium alkylarylether WO 95!30720 PCT1US95103381 sulfate; e.g., TritonT"' W/30, available from Rohm and Haas, alkylarylpolyether sulfates such as alkylarylpoly(ethylene oxide)- sulfates, preferably those A
having up to about 4 ethyleneoxy repeat units, and alkyl sulfates such as sodium lauryl sulfate, ammonium lauryl r sulfate, triethanolamine lauryl sulfate, and sodium hexadecyl sulfate, alkyl ether sulfates such as ammonium lauryl ether sulfate, and-alkylpolyether-sulfates such as alkyl poly-(ethylene oxide) sulfates, preferably those having up to about 4 ethyleneoxy units. Alkyl sulfates, alkyl ether sulfates, alkylarylether sulfates-and mixtures thereof are-preferred as they provide a maximum void volume per micraparticle for-a minimum amount of surfactant. Nonionic emulsifiers, e.g:, SiponicTM Y-500-70 (ethoxylated oleyl alcohol), commercially-available from Alcolac, Inc, and PluronicTM P103 (a block copolymer of polypropylene oxide and polyethylene oxide commercially from BASF Corporation) can be utilized alone or in conjunction with anionic emulsifiers. Polymeric stabilizers may also be present but are not necessary.
The composition may also contain a crosslinking agent such as a multifunctional -(meth)acrylate, e.g:, butanediol diacrylate or hexanediol diacrylate, or other multifunctional crosslinker such as divinylbenzene. When used, crosslinker(s) is (are) added at a level of up to 1 percent, preferably up to 0.5 percent, of the total-polymerizable composition.
Solid microparticles also useful in tapes of the invention may be made by a similar one-step process comprising aqueous suspension polymerization-of at least -one alkyl (meth)acrylate ester monomer or vinyl ester monomer, at least one polar monomer and a polymer - -electrolyte base polymer in the presence of an-suspension stabilizer. St is not necessary to use a high HLB
WO 95!30720 6 -13- .
emulsifier because the droplets formed need not be cavity-containing droplets. Examples of such useful lower HLB emulsifiers include ammonium lauryl sulfate such as Standapol'M A, available from Hercules and other-s steric or-electrosteric polymeric stabilizers such as (poly)vinyl alcohol, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyvinyl methylether, and the like.
Microsphere preparation may be modified by withholding the addition or alloy part of the polymer electrolyte base polymer, and polar monomers until after polymerization of the oil phase is initiated; however, the components must be added to the polymerizing mixture prior to 100$ polymer conversion.
. Discrete conductive polymeric microparticles may also be prepared via suspension polymerizations disclosed in U.S. Pat. No. 3,691,140, US 4,166,152, US 4,636,432, US 4,656,218, and US 5,045,569, for preparing adhesive compositions.
The conductive microparticles-are normally tacky, elastomeric, insoluble but swellable in organic solvents, and small, typically having diameters of at least 1 micrometer, preferably in the range of 1 to 250 micrometers, more preferably from about 1 to 50 micrometers. -They may be solid, contain a single void, or multiple voids.
Following polymerization, an aqueous suspension of the microparticles is obtained which is stable to agglomeration or coagulation under room temperature conditions. The suspension may have non-volatile solids contents of from 10 to 50 percent by weight. Upon prolonged standing, the suspension separates into two phases, one phase being aqueous and substantially free of polymer, the other phase being an aqueous suspension of conductive microparticles. Where high I-ZLB emulsifiers -WO 95130720 L ~ 3 7 316 PCT~S95~03381 -lA-are used the droplets have one or more cavities which, upon drying, become voids. Both phases may contain a minor portion of small latex particles. Decantation of A
the microparticle-rich phase provides an aqueous suspension having a non-volatile solids content on the P
order of about 40-SO percent which, if shaken with water, will readily redisperse. -The adhesion properties-of the microparticles-iday be altered by addition of tackifying resin and/or plasticizer. --Preferred tackifiers for use herein include-hydrogenated rosin esters commercially available from companies such as Hercules Inc., under such trade names as ForalT"' 65, ForalT"' 85, ForalTM 105, and Tacolyn'iM.
Other useful tackifiers include those based on t-butyl styrene. Useful plasticizers include dioctyl phthalate, 2-ethyl hexyl phosphate, tricresyl phosphate, and the like.
It is also within the scope of this invention to include various other components to the adhesives used in tapes of the invention, such as pigments, fillers, including additional conductive fillers, stabilizers; or various polymeric additives.
Tapes of the invention may be produced by coating microparticle-containing compositions of the invention onto a variety of high-temperature resistant primed substrates. Suitable substrates includepolymeric-films such as polyimide and poly-phenylene sulfide, heat-treated non-wovens, fiberglass, metallized polymeric film, ceramic sheet-material, metal foils, etc. The substrate, or tape backing, as it is sometimes called, must be able to withstand temperatures of at -least 200°C
and preferably about 260°C, without degrading or releasing the adhesive from the surface.
WO 95130720 2 7 8 7 3 i 6 PCT/fS95103381 The surfaces) bearing the microparticulate adhesive thereon are primed surfaces. Primers useful in tapes of the invention comprise at least one phenolic resin and at least one rubbery component.
Useful rubbery components include natural rubbers a such as butyl rubbers, and various synthetic compounds, including but not limited to, acrylonitrile-butadiene, acrylonitrile-butadiene-styrene copolymers, styrene-butadiene-styrene, styrene-ethylene butylene-styrene, polychloroprene, polybutadiene, polyisoprene, styrene-isoprene-styrene, and mixtures thereof. Preferred primers contain mixtures of two or more rubbery compounds, such as acrylonitrile-butadiene and , polychloroprene.
Useful phenolic resins, include but are not limited to, phenol formaldehyde resin, available commercially from Union Carbide under- the trade names UCAR BKR-2620, and UCAR CK-1635, novolak resins and the like, and mixtures thereof. Preferred primers contain from 40 to 120, preferably from 40 to 100 parts of phenolic resin per 100 parts of rubbery compound.
The primer may further comprise additives such as tackifying agents, antioxidants, colorants, viscosity adjusting agents, solvents and other conventional additives, which may be used in such amounts as are known in the art.
Preferred tackifying agents include hydrogenated rosin esters, include those available from Hercules under such trade names as Piccolyte'M, Foral"~
Pental nTM
and , y , the like.
Preferred primers include from 15 to 100 parts of tackifier.
Coating of the adhesive and the primer may be carried out by conventional methods such as knife coating, Meyer bar coating, and other conventional means WO 95130720 , L 18 7 316 PC'TJU595103381 -ls-known in the art for coatingadhesives such as use of an extrusion die.
The tape may be commercialized in roll-form, or may a be divided into segments for-sale, such as strips or labels. Additionally, the adhesive may be provided between two substrates, e.g., the adhesive is coated onto a polyimide substrate, which may be provided on a low adhesion backsize or other easily removable surface for individual use.
These and other aspects of the invention are illustrated by the following_examples which should not be viewed as limiting in scope=
Glossary IOA Isooctyl Acrylate AA Acrylic Acid PEO Polyethylene Oxide PEO (750) Acrylate terminated PEO having a MW
of about 750) BPER 70~ Benzoyl Peroxide, Lucidol'M 70 PEODMA Polyethylene Oxide Dimethacrylate [(PEO)sDMA]
1,6 HDDA 1,6 Hexanedinl Diacrylate ALS Ammonium Lauryl Sulfate-Standapol'!M A Ammonium Lauryl Sulfate from Hercules Santivar A Antioxidant di-tertiary amyl hydroquinone PiccolyteT"' 5115 Polyterpene resin (tackifier) ZirexTM Zinc Resinate (tackifier) ' WO 95f30720 218 7 316 PCf/US95/0338I
Phenolic Resins:
CK-1635 Phenol-Formaldehyde Resin, also designated CK-1635 UCAR, manufactured by Union Carbide BKR-2620 Phenol-Formaldehyde Resin, also designated BKR-2620 UCAR, manufactured by Union Carbide.
Test Methods Tribocharging Measurements of Antistatic Coatings The separation of materials which have been laminated to each other causes the generation of electrical charge on the surfaces which were previously in contact. It is possible to calculate the magnitude of the electrical charge as a measure of volts generated.
Voltages were conveniently measured using a 3M 711 Charge Analyser, available from Minnesota Mining and Manufacturing Co. This equipment includes a voltage sensor, mounted in a suitable enclosure. The enclosure is provided with a digital read-out of voltage measured with respect to a stainless steel plate which is horizontally disposed and insulatively attached above the enclosure. Static charge development may be measured for adhesive tapes of the invention by laminating the tape with its adhesive face in contact with the surface of the stainless steel plate.
A strip of tape, 1.0" wide x 6.0" long is applied to the upper surface of the stainless steel plate using a 3 1b roller. The steel plate is then grounded to zero the digital display. Next, a free end of the tape is grasped and using a uniformly applied force, the tape is peeled away from the surface of the steel plate at a rate of 1.0 ft/sec. The voltage developed on the steel plate is displayed via digital read-out. After this reading is noted, the detector is zeroed by grounding the steel WO 95!30720 218 7 31 b PCTIUS95103351 plate. The tape which was previously peeled frDm the steel plate, is-next positioned as close as possible. to the steel plate without touching it. A second reading of voltage is displayed which represents the voltage residing on the surface of the tape.
It is possible to determine the voltage generated during separation of adhesive tapes of the invention from a printed circuit board by attachment of a suitable board to the surface of the stainless steel plate.- Adhesive tape is then attached to the-circuit board us.~ng the procedure.described previously for the steel plate. Upon peeling the tape from th= circuit board a voltage reading is displayed which reflects the charge generated on the surface of the circuit beard_ ,-Following the-process of zeroing the instrument,-by grounding, the residual charge on the tape is measured by positioning the peeled tape in close proximity to the steel-plate.
Tribocharging during unwind of a roll of !.ape is also measured using the 3?rI 711 Charge Analyser. In_this case a length of tape approximately 1.0 ft. long is, unwound from a roll of adhesive tape but not removed from it. When the unwound length is placed in close proximity to the previously grounded steel plate, a voltage reading is displayed which represents the magnitude of the charge on the tape.
Adhesive Transfer _ With tapes of the current invention it ~is important to prevent adhesive transfer from the tape onto the surface of electronic assemblies which are subject to wave soldering. The test measures the ability of the tape to maintain a strong bond between film support and -adhesive even at the elevated temperature of molten solder-. _ WO 95130720 218 7 316 PCT~S95/03381 A tape sample (2.5 cm x 7.6 cm) is applied with its adhesive in contact with the surface of a 4.45 cm x lOcm section of dust-free printed circuit board (PCB). A
small portion of the tape overlaps an edge portion of the PCB to facilitate subsequent removal. Pressure from a 3 s 1b roller assures consistent application of the tape samples. These test pieces are then positioned in a molten solder bath so that the tape is held below the surface of the solder for a desired length of time.
1O After removal from the solder bath, the test pieces are allowed to cool to rowm temperature. The free end of the tape is grasped and .irawn away from the edge of the PCB. Observation is made to determine if the adhesive separates from the film rapport, thereby leaving an un-wanted residue on the surface of the PCB.
xamples Preparations ef Microparticles _Example 1 Acrylic acid (5.4g), polyethylene oxide acrylate (PEO 750) (13.5q), PEODMA (O.ISg) and 70$ benzoyl peroxide (0.99g) were dissolved in isooctyl acrylate (223.2g). This solution was added to an aqueous solution of surfactant. The surfactant solution comprised StandapolT"sA, available from Hercules, (8.4g) dissolved in de-ionized water (360g). An emulsion of the isooctyl acrylate solution in the aqueous solution was produced by high shear mixing using an Omni mixer at setting 5.
Mixing was continued until the average particle size of the oily droplets was approximately 3Etm. Size was determined using an optical microscope.
The resulting oil-in-water emulsion was charged to a -1-liter resin reactor equipped with four baffles, a paddle stirrer and a suitable heat source, such as a R'O 95130720 ~ 18 7 316 PCT/US95103381 _20_ heating mantle. With continuous stirring at a rate of 400 rpm, the reactor and contents were heated to 60°C.
At this point the reactor was degassed with nitrogen. A reaction proceeded in the absence of oxygen.
This was allowed to continue for a period of 22 hours J
while both temperature and stirring rate were maintained.
The resulting aqueous suspension contained insoluble particles of approximately SEun in diameter.
Example 2. .... _. .m.
Primer Composition for Polyimide Substrate Ingred. Parts ~ solids Butadiene/Acrylonitrile 75.00 parts 25.63 Neoprene W. 25.00 parts 8.54 Phenolic Resin BKR-2620 19.90 parts 6.8 Santivar A 3.95 parts 1.35 Piccolyte 5115 - 49.67 parts 16.97 Zirex 49.67 parts 16.97 Phenolic Resin 69.43 parts 23.73 Methyl Ethyl Ketone 329.57 parts iso-Propanol 60.00 parts Toluene - 621.00 parts PhVSical Properties.,. __., _r, .
S.G. of Solids 1.065 S.G. of Solution 0.884 # per Gallon 7.370 ~ Comb. RHC Soln. 7-.67 ~ Comb. RHC on Solids 34.17 ~ Theoretical Solids22.45 Preparation of Primer Solufion Materials .
Butadiene/Acrylonitrile 75.00 parts 5.755 ,.
NeopreneTM W. 25.00 parts -- 1.918 Phenolic Resin BKR-2620 19.90 parts 1.527 Santivar'""- A 3. 95 darts 0. 303~-Piccolyte'M SlIS 49.67 parts 3.811$
WO 95130720 218 7 31 b Zirex'M 49.67 parts 3.811$
Phenolic Resin 69.43 parts 5.328$
Methyl Ethyl Ketone 329:57 parts 25.290$
iso-Propanol 60.00 parts 4.604$
Toluene 621.00 parts 47.652$
The resins, tackifiers and antioxidant, indicated above, are dissolved in a mixed solvent comprising methyl ethyl ketone, iso-propanol and toluene to provide a primer coating for film supports. Conventional churns, equipped withstirrers, or similar equipment may be used for primer solution preparation. The solution is inspected for clarity and filtered if necessary.
Example 3 Adhesive Coatin Composition Adhesives 100 parts Lithium Nitrate 0.40 parts Lithium Hydroxide 0.28 parts Ammonium Hydroxide 0.60 parts Benzotriazole2 0.05 parts Thickener (QA 708)' 0.30 parts ' 40$ solids suspension of Ex. 1 Z 10$ soln, in 1:1 IPA/Water 3 50$ soln. in IPA
To 100 parts of the adhesive, prepared as previously described, was added a combination of lithium salts, to . 30 increase ionic conductivity, ammonium hydroxide for pH
adjustment, benzotriazole for corrosion inhibition and a thickener to improve coating characteristics. Each of the additional ingredients was slowly stirred into the adhesive composition and thoroughly mixed prior to coating.
Example 4 Tape Preparation Using A Primer Coating The high temperature resistant, antistatic adhesive tape of the present invention was prepared by coating suitable film supports with a primer, which, after drying, was over-coated with a layer of the antistatic adhesive composition.
The primer composition was used as previously described or with addition of 0.5 parts of benzotriazole corrosion protection agent. A knurled roll applied a coating of primer on a 20 ~.~m (1 mil) filled polyimide (Kapton) film. The coated film was dried at 180°F for 1 min. with a resulting primer coating weight of 0.003 gm/sq. ft.
A 75 ~zm (3 mil) film of adhesive was then coated over the primer layer then dried for 3 mins. at 110°C
(230°F) .
Examples 5-lOC
Tape Properties The electrical and adhesive properties of tapes including the invention are presented in the following table.
Examples 5, C6 and C7 were tested at 10$ relative humidity while samples 8, C9 and C10 were tested at a0°
relative humidity.
Examples 5 and 8 are tapes of the current invention.
Examples C6 and C9 comprise a commercially available tape known as 3M ##92 Tape which has a silicone adhesive.
Examples C7 and C10 are a commercially available tape known as 3M #1205.
Note that only the tapes of the invention exhibit both lack of adhesive transfer and low tribocharging.
W O 95130720 2 l 8 7 316 PCT~S95103381 Tape ConductivityTribocharge Adhesive Identity Ohms/sq. Volts Transfer*
(3M Tester...$711) Unwind Removal from PC Board Ex. S 4.8 X 109 3.0 35 No transfer Ex. 6C 1.3 x 101 >2000 670 No transfer Ex. C7 2.7 x 10'5 ,1919 680 > 30B Transfer Ex. B 2.7 x 108 2 4 No transfer Ex. 9C 2.3 x lOlA 1311 - 581 No transfer I Ex. C10 5.8 x 1015 1223. 566 > 30~ Transfer I
* Adhesive transfer was measured at 287°C (550°F) with tape samples dipped into molten solder for 5 seconds.
means the group containing the electron donating species.
The term "microparticle" means a particle having a diameter of from 1 micrometer to 250 micrometers.
4- The term "tribocharging" means electrostatic charge generation associated with friction or separation between separable surfaces.
5. The term "droplet" means the liquid stage of the microparticles prior to the completion of polymerization.
6. The term "cavity" means a space within the walls of a droplet or microparticle when still in the suspension or dispersion medium prior to drying, and thus containing whatever medium was used.
7. The term "void" means an empty space completely within the walls of a polymerized microparticle.
g_ The term "hollow"means containing at least one void or cavity.
g. The term "solid" means voids or cavity-free.
10. The term alkyl (meth)acrylate means an alkyl acrylate or alkyl methacrylate.
11. The term "modified surface" means a surface which has been subjected to a priming, coating or treatment such as chemical or radiation treatment such that the original properties of the surface have been changed.
As used herein, all parts, percents, and ratios are by weight, unless specifically stated otherwise.
Detailed Description of the Invention Alkyl acrylate or methacrylate monomers useful in preparing the microparticles and conductive pressure-sensitive adhesives for use in tapes of this invention are those monofunctional unsaturated acrylate or methacrylic esters of non-tertiary alkyl alcohols, the alkyl groups of which have from 4 to about 14 carbon atoms. Such acrylates.are oleophilic, water emulsifiable, have limited water solubility, and as homopolymers, generally have glass transition temperatures below about -20°C. Included within this class of monomers are, for example, isooctyl acrylate, 4-methyl-2-pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, sec-butyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isodecyl methacrylate, isononyl acrylate, isodecyl acrylate, and the like, singly or in mixtures.
Preferred acrylates include isooctyl acrylate, isononyl acrylate, isoamyl acrylate, isodecyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, sec-butyl acrylate, and mixtures thereof. Acrylate or methacrylate or other vinyl monomers which, as homopolymers, have glass transition temperatures higher than about -20°C, e.g., tert-butyl acrylate, vinyl acetate, and the like, may be utilized in conjunction with one or more of the acrylate or methacrylate monomers provided that the glass transition temperature of the resultant polymer is below about -20°C. When methacrylate monomer is the sole alkyl acrylate utilized, a crosslinking agent, infra, must be included.
Useful vinyl ester monomers are those which form homopolymers having glass transition temperatures below about 10°C. Such esters comprise 2 to 14 carbon atoms, and includes such monomers as vinyl 2-ethylhexanoate, WO 95/30720 ? ~ g 7 3 ~ 6 PCTIUS95103381 -g-vinyl caprate, vinyl laurate,vinyl pelargonate, vinyl hexanoate, vinyl propionate, vinyl decanoate, vinyl octanoate, and the like.
r Useful polar monomers include moderately polar monomers such as N-vinyl-2-pyrrolidone, N-vinyl a caprolactam, acrylonitrile, vinyl acrylate, ahd diallyl .
phthalate, as well as strongly polar monomers such as acrylic--acid, methacrylic acid, itaconic-acid, hydroxyalkyl acrylates, cyanoalkyl acrylates, acrylamides, substituted acrylamides. When more than one polar monomer is used, mixtures may include monomers-having similar or unlike polarities, e.g., one moderately polar and one strongly polar monomer or two monomers from-one group.
The conductive microparticles and the pressure-sensitive adhesives made therefrom comprise at least 70 parts by weight of at least one alkyl (meth)acrylate ester or vinyl ester and correspondingly, up to 30 parts by weight of one or more polar monomers.
Polymer electrolyte base polymers suitable for-use include polyethylene oxide, polyphenylene oxide, polyphenylene sulfide, polyethylene sulfide, polyethyleneimine, polypropylene oxide, polybutylene oxide, polybutylene sulfide, polybutylene imine, and the like. Polyethylene oxide is preferred. Useful amounts of the polymer electrolyte base polymer in microparticles of the invention range from 0.1 part to 10 parts, preferably from 1 part to 5 parts, based on LDO parts monomer weight.
The conductive properties of. the polymeric microparticles may be further enhanced by the addition of ionic salts to adhesive compositions which contain the microparticles. It is believed that the ionic salts become associated with the electron donatinggroups present in the amorphous polymer domains.
WO 95130720 2 ~ ~ 7 3 i ~ PCTlUS95103381 _9_ Salts used for this purpose include salts of alkali metals, and alkaline earth metals, including but not limited to, NaI, NaSCN, BaCF3Sos, NaBr, NaC109, LiCl, LiN03, L1CF3SO3, LiS04, LiOH and KOH. Lithium salts are preferred for the present invention, especially lithium nitrate.
Microparticles may v~e prepared by various emulsification processes, which are varied depending on whether hollow or solid microparticles are desired.
Aqueous suspensions of hollow microparticles may be prepared by a "two-step" emulsification process which first involves forming a water-in-oil emulsion of an aqueous solution of polax- monomers) in oil phase monomer,--i.e., at least cne (meth)acrylate or vinyl ester monomer, with a polymer electrolyte base polymer, using an emulsifier having a lcw hydrophilic-lipophilic balance (HLB) value. Suitable emulsifiers are those having an HLB value below about 7, prefer<:bly in the range of about 2 to about 7. Examples cf-such emulsifiers include sorbitan monooleate, sorbitan trioleate, and ethoxylated oleyl alcohol such as Brij'M 93, available from Atlas Chemical Industries, Inc.
J
WO 95!30720 2 J g ~ 3 ~ a PCTIUS95103381 Thus, in this first step, oil phase monomer(s), polymer electrolyte base polymer, emulsifier, a free-radical initiator, and, optionally, a crosslinking r monomer or monomers as defined below are-combined, and an aqueous solution of all or a-portion of the polar monomers) is agitated and poured into the oil phase mixture to form a water-in-oil emulsion. The polymer electrolyte base polymer may be added to either the-oil -phase or the water-phase. A thickening agent, e.g.~-methyl cellulose may also be included in theaqueous phase of the water-in-oil emulsion. In the s-econd step, a water-in-oil-in-water emulsion is formed by dispersing the water-in-oil emulsion of_the first step into an aqueous phasecontaining an emulsifier-having-an HLB
value above about 6. The aqueous phase may also contain any portion of -the polar monomers) which-was not added in step-one. Examples of such-emulsifiers include ethoxylated sorbitan monooleate, ethoxylated-lauryl alcohol, and alkyl sulfates. In both steps, when an emulsifier is-utilized, its concentration should be-greater than its critical-micelle-concentration, which is herein defined as the minimum concentration of emulsifier necessary for the formation of micelles, i.e.,sub-microscopic aggregations of emulsifier molecules.
Critical micelle concentration is slightly different for each emulsifier; usable concentrations ranging from 1.0 x 10-' to about 3.0 moles/liter. Additional detail concerning the preparation of water-in-oil-in-water,-emulsions, i.e., multiple emulsions, may be found in various literature references, e.g., Surfactant Systems:
Their Chemistry, Pharmacy, & Biology, (D. Attwood and A.
T. Florence, Chapman & Hall-Ztd, New York City, 1983).
The final process step of this method involves-the application of heat or radiation to initiate polymerization of the monomers. Useful initiators are WO 95130720 218 7 316 p~/pS95/0338I
those which are normally suitable for free radical polymerization of acrylate or vinyl ester monomers and which are oil-soluble and of-very low solubility in water. However, when the polar monomer is N-vinyl pyrrolidone, the use of benzoyl peroxide as the initiator is recommended.
Examples of such initiators include azo compounds, hydropex-oxides, peroxides, and the like, and photoinitiators such as benzophenone, benzoin ethyl ether, and 2,2-dimethoxy-2-phenyl acetophenone.
Use of a water-soluble polymerization initiator causes formation of substantial amounts of-latex. The extremely small particle size of latex particles renders any significant formation of latex undesirable. The initiator is generally used in an amount ranging from 0.01 percent up to 10 percent by weight of the total polymerizable composition, preferably up to 5 percent.
Aqueous suspensions of hollow conductive microparticles may also by prepared by a "one-step"
emulsification process. comprising aqueous suspension polymerization of at least one alkyl (meth)acrylate ester monomer or vinyl ester monomer and at least one polar monomer and a polymer electrolyte base polymer in the presence of at least one emulsifier capable of producing a water-in-oil emulsion inside the droplets which is substantially stable during emulsification and polymerization.- As in the two-step emulsification process, the emulsifier is utilized in concentrations greater than its critical micelle concentration. In _ 30 general, high HLB emulsifiers are required, i.e., emulsifiers having an HLB value of at least about 25, will produce stable cavity-containing droplets during the polymerization, and are-suitable for use in this one-step process. Examples of such emulsifiers include alkylarylether sulfates such as sodium alkylarylether WO 95!30720 PCT1US95103381 sulfate; e.g., TritonT"' W/30, available from Rohm and Haas, alkylarylpolyether sulfates such as alkylarylpoly(ethylene oxide)- sulfates, preferably those A
having up to about 4 ethyleneoxy repeat units, and alkyl sulfates such as sodium lauryl sulfate, ammonium lauryl r sulfate, triethanolamine lauryl sulfate, and sodium hexadecyl sulfate, alkyl ether sulfates such as ammonium lauryl ether sulfate, and-alkylpolyether-sulfates such as alkyl poly-(ethylene oxide) sulfates, preferably those having up to about 4 ethyleneoxy units. Alkyl sulfates, alkyl ether sulfates, alkylarylether sulfates-and mixtures thereof are-preferred as they provide a maximum void volume per micraparticle for-a minimum amount of surfactant. Nonionic emulsifiers, e.g:, SiponicTM Y-500-70 (ethoxylated oleyl alcohol), commercially-available from Alcolac, Inc, and PluronicTM P103 (a block copolymer of polypropylene oxide and polyethylene oxide commercially from BASF Corporation) can be utilized alone or in conjunction with anionic emulsifiers. Polymeric stabilizers may also be present but are not necessary.
The composition may also contain a crosslinking agent such as a multifunctional -(meth)acrylate, e.g:, butanediol diacrylate or hexanediol diacrylate, or other multifunctional crosslinker such as divinylbenzene. When used, crosslinker(s) is (are) added at a level of up to 1 percent, preferably up to 0.5 percent, of the total-polymerizable composition.
Solid microparticles also useful in tapes of the invention may be made by a similar one-step process comprising aqueous suspension polymerization-of at least -one alkyl (meth)acrylate ester monomer or vinyl ester monomer, at least one polar monomer and a polymer - -electrolyte base polymer in the presence of an-suspension stabilizer. St is not necessary to use a high HLB
WO 95!30720 6 -13- .
emulsifier because the droplets formed need not be cavity-containing droplets. Examples of such useful lower HLB emulsifiers include ammonium lauryl sulfate such as Standapol'M A, available from Hercules and other-s steric or-electrosteric polymeric stabilizers such as (poly)vinyl alcohol, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyvinyl methylether, and the like.
Microsphere preparation may be modified by withholding the addition or alloy part of the polymer electrolyte base polymer, and polar monomers until after polymerization of the oil phase is initiated; however, the components must be added to the polymerizing mixture prior to 100$ polymer conversion.
. Discrete conductive polymeric microparticles may also be prepared via suspension polymerizations disclosed in U.S. Pat. No. 3,691,140, US 4,166,152, US 4,636,432, US 4,656,218, and US 5,045,569, for preparing adhesive compositions.
The conductive microparticles-are normally tacky, elastomeric, insoluble but swellable in organic solvents, and small, typically having diameters of at least 1 micrometer, preferably in the range of 1 to 250 micrometers, more preferably from about 1 to 50 micrometers. -They may be solid, contain a single void, or multiple voids.
Following polymerization, an aqueous suspension of the microparticles is obtained which is stable to agglomeration or coagulation under room temperature conditions. The suspension may have non-volatile solids contents of from 10 to 50 percent by weight. Upon prolonged standing, the suspension separates into two phases, one phase being aqueous and substantially free of polymer, the other phase being an aqueous suspension of conductive microparticles. Where high I-ZLB emulsifiers -WO 95130720 L ~ 3 7 316 PCT~S95~03381 -lA-are used the droplets have one or more cavities which, upon drying, become voids. Both phases may contain a minor portion of small latex particles. Decantation of A
the microparticle-rich phase provides an aqueous suspension having a non-volatile solids content on the P
order of about 40-SO percent which, if shaken with water, will readily redisperse. -The adhesion properties-of the microparticles-iday be altered by addition of tackifying resin and/or plasticizer. --Preferred tackifiers for use herein include-hydrogenated rosin esters commercially available from companies such as Hercules Inc., under such trade names as ForalT"' 65, ForalT"' 85, ForalTM 105, and Tacolyn'iM.
Other useful tackifiers include those based on t-butyl styrene. Useful plasticizers include dioctyl phthalate, 2-ethyl hexyl phosphate, tricresyl phosphate, and the like.
It is also within the scope of this invention to include various other components to the adhesives used in tapes of the invention, such as pigments, fillers, including additional conductive fillers, stabilizers; or various polymeric additives.
Tapes of the invention may be produced by coating microparticle-containing compositions of the invention onto a variety of high-temperature resistant primed substrates. Suitable substrates includepolymeric-films such as polyimide and poly-phenylene sulfide, heat-treated non-wovens, fiberglass, metallized polymeric film, ceramic sheet-material, metal foils, etc. The substrate, or tape backing, as it is sometimes called, must be able to withstand temperatures of at -least 200°C
and preferably about 260°C, without degrading or releasing the adhesive from the surface.
WO 95130720 2 7 8 7 3 i 6 PCT/fS95103381 The surfaces) bearing the microparticulate adhesive thereon are primed surfaces. Primers useful in tapes of the invention comprise at least one phenolic resin and at least one rubbery component.
Useful rubbery components include natural rubbers a such as butyl rubbers, and various synthetic compounds, including but not limited to, acrylonitrile-butadiene, acrylonitrile-butadiene-styrene copolymers, styrene-butadiene-styrene, styrene-ethylene butylene-styrene, polychloroprene, polybutadiene, polyisoprene, styrene-isoprene-styrene, and mixtures thereof. Preferred primers contain mixtures of two or more rubbery compounds, such as acrylonitrile-butadiene and , polychloroprene.
Useful phenolic resins, include but are not limited to, phenol formaldehyde resin, available commercially from Union Carbide under- the trade names UCAR BKR-2620, and UCAR CK-1635, novolak resins and the like, and mixtures thereof. Preferred primers contain from 40 to 120, preferably from 40 to 100 parts of phenolic resin per 100 parts of rubbery compound.
The primer may further comprise additives such as tackifying agents, antioxidants, colorants, viscosity adjusting agents, solvents and other conventional additives, which may be used in such amounts as are known in the art.
Preferred tackifying agents include hydrogenated rosin esters, include those available from Hercules under such trade names as Piccolyte'M, Foral"~
Pental nTM
and , y , the like.
Preferred primers include from 15 to 100 parts of tackifier.
Coating of the adhesive and the primer may be carried out by conventional methods such as knife coating, Meyer bar coating, and other conventional means WO 95130720 , L 18 7 316 PC'TJU595103381 -ls-known in the art for coatingadhesives such as use of an extrusion die.
The tape may be commercialized in roll-form, or may a be divided into segments for-sale, such as strips or labels. Additionally, the adhesive may be provided between two substrates, e.g., the adhesive is coated onto a polyimide substrate, which may be provided on a low adhesion backsize or other easily removable surface for individual use.
These and other aspects of the invention are illustrated by the following_examples which should not be viewed as limiting in scope=
Glossary IOA Isooctyl Acrylate AA Acrylic Acid PEO Polyethylene Oxide PEO (750) Acrylate terminated PEO having a MW
of about 750) BPER 70~ Benzoyl Peroxide, Lucidol'M 70 PEODMA Polyethylene Oxide Dimethacrylate [(PEO)sDMA]
1,6 HDDA 1,6 Hexanedinl Diacrylate ALS Ammonium Lauryl Sulfate-Standapol'!M A Ammonium Lauryl Sulfate from Hercules Santivar A Antioxidant di-tertiary amyl hydroquinone PiccolyteT"' 5115 Polyterpene resin (tackifier) ZirexTM Zinc Resinate (tackifier) ' WO 95f30720 218 7 316 PCf/US95/0338I
Phenolic Resins:
CK-1635 Phenol-Formaldehyde Resin, also designated CK-1635 UCAR, manufactured by Union Carbide BKR-2620 Phenol-Formaldehyde Resin, also designated BKR-2620 UCAR, manufactured by Union Carbide.
Test Methods Tribocharging Measurements of Antistatic Coatings The separation of materials which have been laminated to each other causes the generation of electrical charge on the surfaces which were previously in contact. It is possible to calculate the magnitude of the electrical charge as a measure of volts generated.
Voltages were conveniently measured using a 3M 711 Charge Analyser, available from Minnesota Mining and Manufacturing Co. This equipment includes a voltage sensor, mounted in a suitable enclosure. The enclosure is provided with a digital read-out of voltage measured with respect to a stainless steel plate which is horizontally disposed and insulatively attached above the enclosure. Static charge development may be measured for adhesive tapes of the invention by laminating the tape with its adhesive face in contact with the surface of the stainless steel plate.
A strip of tape, 1.0" wide x 6.0" long is applied to the upper surface of the stainless steel plate using a 3 1b roller. The steel plate is then grounded to zero the digital display. Next, a free end of the tape is grasped and using a uniformly applied force, the tape is peeled away from the surface of the steel plate at a rate of 1.0 ft/sec. The voltage developed on the steel plate is displayed via digital read-out. After this reading is noted, the detector is zeroed by grounding the steel WO 95!30720 218 7 31 b PCTIUS95103351 plate. The tape which was previously peeled frDm the steel plate, is-next positioned as close as possible. to the steel plate without touching it. A second reading of voltage is displayed which represents the voltage residing on the surface of the tape.
It is possible to determine the voltage generated during separation of adhesive tapes of the invention from a printed circuit board by attachment of a suitable board to the surface of the stainless steel plate.- Adhesive tape is then attached to the-circuit board us.~ng the procedure.described previously for the steel plate. Upon peeling the tape from th= circuit board a voltage reading is displayed which reflects the charge generated on the surface of the circuit beard_ ,-Following the-process of zeroing the instrument,-by grounding, the residual charge on the tape is measured by positioning the peeled tape in close proximity to the steel-plate.
Tribocharging during unwind of a roll of !.ape is also measured using the 3?rI 711 Charge Analyser. In_this case a length of tape approximately 1.0 ft. long is, unwound from a roll of adhesive tape but not removed from it. When the unwound length is placed in close proximity to the previously grounded steel plate, a voltage reading is displayed which represents the magnitude of the charge on the tape.
Adhesive Transfer _ With tapes of the current invention it ~is important to prevent adhesive transfer from the tape onto the surface of electronic assemblies which are subject to wave soldering. The test measures the ability of the tape to maintain a strong bond between film support and -adhesive even at the elevated temperature of molten solder-. _ WO 95130720 218 7 316 PCT~S95/03381 A tape sample (2.5 cm x 7.6 cm) is applied with its adhesive in contact with the surface of a 4.45 cm x lOcm section of dust-free printed circuit board (PCB). A
small portion of the tape overlaps an edge portion of the PCB to facilitate subsequent removal. Pressure from a 3 s 1b roller assures consistent application of the tape samples. These test pieces are then positioned in a molten solder bath so that the tape is held below the surface of the solder for a desired length of time.
1O After removal from the solder bath, the test pieces are allowed to cool to rowm temperature. The free end of the tape is grasped and .irawn away from the edge of the PCB. Observation is made to determine if the adhesive separates from the film rapport, thereby leaving an un-wanted residue on the surface of the PCB.
xamples Preparations ef Microparticles _Example 1 Acrylic acid (5.4g), polyethylene oxide acrylate (PEO 750) (13.5q), PEODMA (O.ISg) and 70$ benzoyl peroxide (0.99g) were dissolved in isooctyl acrylate (223.2g). This solution was added to an aqueous solution of surfactant. The surfactant solution comprised StandapolT"sA, available from Hercules, (8.4g) dissolved in de-ionized water (360g). An emulsion of the isooctyl acrylate solution in the aqueous solution was produced by high shear mixing using an Omni mixer at setting 5.
Mixing was continued until the average particle size of the oily droplets was approximately 3Etm. Size was determined using an optical microscope.
The resulting oil-in-water emulsion was charged to a -1-liter resin reactor equipped with four baffles, a paddle stirrer and a suitable heat source, such as a R'O 95130720 ~ 18 7 316 PCT/US95103381 _20_ heating mantle. With continuous stirring at a rate of 400 rpm, the reactor and contents were heated to 60°C.
At this point the reactor was degassed with nitrogen. A reaction proceeded in the absence of oxygen.
This was allowed to continue for a period of 22 hours J
while both temperature and stirring rate were maintained.
The resulting aqueous suspension contained insoluble particles of approximately SEun in diameter.
Example 2. .... _. .m.
Primer Composition for Polyimide Substrate Ingred. Parts ~ solids Butadiene/Acrylonitrile 75.00 parts 25.63 Neoprene W. 25.00 parts 8.54 Phenolic Resin BKR-2620 19.90 parts 6.8 Santivar A 3.95 parts 1.35 Piccolyte 5115 - 49.67 parts 16.97 Zirex 49.67 parts 16.97 Phenolic Resin 69.43 parts 23.73 Methyl Ethyl Ketone 329.57 parts iso-Propanol 60.00 parts Toluene - 621.00 parts PhVSical Properties.,. __., _r, .
S.G. of Solids 1.065 S.G. of Solution 0.884 # per Gallon 7.370 ~ Comb. RHC Soln. 7-.67 ~ Comb. RHC on Solids 34.17 ~ Theoretical Solids22.45 Preparation of Primer Solufion Materials .
Butadiene/Acrylonitrile 75.00 parts 5.755 ,.
NeopreneTM W. 25.00 parts -- 1.918 Phenolic Resin BKR-2620 19.90 parts 1.527 Santivar'""- A 3. 95 darts 0. 303~-Piccolyte'M SlIS 49.67 parts 3.811$
WO 95130720 218 7 31 b Zirex'M 49.67 parts 3.811$
Phenolic Resin 69.43 parts 5.328$
Methyl Ethyl Ketone 329:57 parts 25.290$
iso-Propanol 60.00 parts 4.604$
Toluene 621.00 parts 47.652$
The resins, tackifiers and antioxidant, indicated above, are dissolved in a mixed solvent comprising methyl ethyl ketone, iso-propanol and toluene to provide a primer coating for film supports. Conventional churns, equipped withstirrers, or similar equipment may be used for primer solution preparation. The solution is inspected for clarity and filtered if necessary.
Example 3 Adhesive Coatin Composition Adhesives 100 parts Lithium Nitrate 0.40 parts Lithium Hydroxide 0.28 parts Ammonium Hydroxide 0.60 parts Benzotriazole2 0.05 parts Thickener (QA 708)' 0.30 parts ' 40$ solids suspension of Ex. 1 Z 10$ soln, in 1:1 IPA/Water 3 50$ soln. in IPA
To 100 parts of the adhesive, prepared as previously described, was added a combination of lithium salts, to . 30 increase ionic conductivity, ammonium hydroxide for pH
adjustment, benzotriazole for corrosion inhibition and a thickener to improve coating characteristics. Each of the additional ingredients was slowly stirred into the adhesive composition and thoroughly mixed prior to coating.
Example 4 Tape Preparation Using A Primer Coating The high temperature resistant, antistatic adhesive tape of the present invention was prepared by coating suitable film supports with a primer, which, after drying, was over-coated with a layer of the antistatic adhesive composition.
The primer composition was used as previously described or with addition of 0.5 parts of benzotriazole corrosion protection agent. A knurled roll applied a coating of primer on a 20 ~.~m (1 mil) filled polyimide (Kapton) film. The coated film was dried at 180°F for 1 min. with a resulting primer coating weight of 0.003 gm/sq. ft.
A 75 ~zm (3 mil) film of adhesive was then coated over the primer layer then dried for 3 mins. at 110°C
(230°F) .
Examples 5-lOC
Tape Properties The electrical and adhesive properties of tapes including the invention are presented in the following table.
Examples 5, C6 and C7 were tested at 10$ relative humidity while samples 8, C9 and C10 were tested at a0°
relative humidity.
Examples 5 and 8 are tapes of the current invention.
Examples C6 and C9 comprise a commercially available tape known as 3M ##92 Tape which has a silicone adhesive.
Examples C7 and C10 are a commercially available tape known as 3M #1205.
Note that only the tapes of the invention exhibit both lack of adhesive transfer and low tribocharging.
W O 95130720 2 l 8 7 316 PCT~S95103381 Tape ConductivityTribocharge Adhesive Identity Ohms/sq. Volts Transfer*
(3M Tester...$711) Unwind Removal from PC Board Ex. S 4.8 X 109 3.0 35 No transfer Ex. 6C 1.3 x 101 >2000 670 No transfer Ex. C7 2.7 x 10'5 ,1919 680 > 30B Transfer Ex. B 2.7 x 108 2 4 No transfer Ex. 9C 2.3 x lOlA 1311 - 581 No transfer I Ex. C10 5.8 x 1015 1223. 566 > 30~ Transfer I
* Adhesive transfer was measured at 287°C (550°F) with tape samples dipped into molten solder for 5 seconds.
Claims (10)
1. A heat-resistant anti-static pressure-sensitive adhesive tape comprising a substrate having opposing surfaces, at least one of said surfaces bearing thereon an acrylic microparticulate adhesive wherein the microparticles have an average diameter of 1 to 250 micrometers, wherein the microparticles have a surface bearing thereon an ionic conductive material formed from a polymer electrolyte base polymer and at least one ionic salt selected from the group consisting of salts of alkali metals and salts of alkaline earth metals, said adhesive being bonded to said substrate by means of a primer, said primer comprising at least one phenolic resin and at least one rubbery compound, said adhesive tape being capable of surviving immersion in molten solder at 260°C for at least 5 seconds.
2. A heat-resistant anti-static pressure-sensitive adhesive tape according to claim 1, wherein said at least one phenolic resin is a phenol-formaldehyde resin.
3. A heat-resistant anti-static pressure-sensitive adhesive tape according to claim 1, wherein said primer coating comprises at least one rubbery compound selected from the group consisting of a butyl rubber, an acrylonitrile-butadiene copolymer, an acrylonitrile-butadiene-styrene copolymer, a styrene-butadiene-styrene copolymer, a styrene-ethylene butylene-styrene copolymer, polychloroprene, polybutadiene, polyisoprene, and a styrene-isoprene-styrene copolymer.
4. A heat-resistant anti-static pressure-sensitive adhesive tape according to claim 1, wherein said primer coating comprises a mixture of acrylonitrile-butadiene-styrene copolymer and polychloroprene.
5. A heat-resistant anti-static pressure-sensitive adhesive tape according to claim 1, wherein said microparticulate adhesive comprises a polymer of monomers comprising:
a) at least 70 parts of at least one alkyl (meth)acrylate or vinyl ester, b) correspondingly, up to 30 parts of at least one polar monomer, to make 100 parts monomer, and wherein said ionic conductive material comprises a polymer electrolyte formed from a polymer electrolyte base polymer selected from the group consisting of polyethylene oxide, polyphenylene oxide, polyphenylene sulfide, polyethylene sulfide, polyethyleneimine, polypropylene oxide, polybutylene oxide, polybutylene sulfide, and polybutylene imine, said polymer electrolyte base polymer is added in an amount of from 0.1 part to 10 parts per 100 parts monomer.
a) at least 70 parts of at least one alkyl (meth)acrylate or vinyl ester, b) correspondingly, up to 30 parts of at least one polar monomer, to make 100 parts monomer, and wherein said ionic conductive material comprises a polymer electrolyte formed from a polymer electrolyte base polymer selected from the group consisting of polyethylene oxide, polyphenylene oxide, polyphenylene sulfide, polyethylene sulfide, polyethyleneimine, polypropylene oxide, polybutylene oxide, polybutylene sulfide, and polybutylene imine, said polymer electrolyte base polymer is added in an amount of from 0.1 part to 10 parts per 100 parts monomer.
6. A heat-resistant anti-static pressure-sensitive adhesive tape according to claim 1, wherein said ionic conductive material comprises from 0.01 moles to 10 moles of at least one salt of an alkali metal or alkaline earth metal per mole of the polymer electrolyte base polymer.
7. A heat-resistant anti-static pressure-sensitive adhesive tape according to claim 6, wherein said salt is selected from the group consisting of LiCl, LiNO3, LiCF3SO3, LiSO4, LiOH, KOH, NaSCN, NaI, BaSO3CF3, and NH4OH.
8. A heat-resistant anti-static pressure sensitive adhesive tape according to claim 5, wherein the at least one alkyl (meth)acrylate comprises one of more component selected from the group consisting of isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isoamyl (meth)acrylate, isodecyl (meth)acrylate, and butyl (meth)acrylate, the at least one vinyl ester comprises one or more component selected from the group consisting of vinyl 2-ethylhexanoate, vinyl caproate, vinyl laurate, vinyl pelargonate, vinyl hexanoate, vinyl propionate, vinyl decanoate, and vinyl octanoate, and the at least one polar monomer comprises one or more component selected from the group consisting of N-vinyl-2-pyrrolidone, N-vinyl caprolactam, acrylonitrile, vinyl acrylate, diallyl phthalate, acrylic acid, methacrylic acid, itaconic acid, an hydroxyalkyl acrylate, a cyanoalkyl acrylate, an acrylamide, and a substituted acrylamide.
9. A heat-resistant anti-static pressure-sensitive adhesive tape according to claim 1, wherein said substrate is selected from the group consisting of polyimide, polyphenylene sulfide, heat-treated non-woven material, fiberglass, metallized polymeric film, ceramic sheet material, and metal foil.
10. A heat-resistant anti-static pressure-sensitive adhesive tape according to claim 9, wherein said substrate is polyimide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US23930994A | 1994-05-06 | 1994-05-06 | |
| US08/239309 | 1994-05-06 | ||
| PCT/US1995/003381 WO1995030720A1 (en) | 1994-05-06 | 1995-03-16 | High temperature resistant antistatic pressure-sensitive adhesive tape |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2187316A1 CA2187316A1 (en) | 1995-11-16 |
| CA2187316C true CA2187316C (en) | 2007-03-13 |
Family
ID=38007981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002187316A Expired - Fee Related CA2187316C (en) | 1994-05-06 | 1995-03-16 | High temperature resistant antistatic pressure-sensitive adhesive tape |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2187316C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608405A (en) * | 2020-12-15 | 2021-04-06 | 深圳市撒比斯科技有限公司 | Polymer for adhesive and application thereof |
-
1995
- 1995-03-16 CA CA002187316A patent/CA2187316C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2187316A1 (en) | 1995-11-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20130318 |