CN106279686A - Composition for forming soluble polyimide, cover film and manufacturing method thereof - Google Patents
Composition for forming soluble polyimide, cover film and manufacturing method thereof Download PDFInfo
- Publication number
- CN106279686A CN106279686A CN201510381484.3A CN201510381484A CN106279686A CN 106279686 A CN106279686 A CN 106279686A CN 201510381484 A CN201510381484 A CN 201510381484A CN 106279686 A CN106279686 A CN 106279686A
- Authority
- CN
- China
- Prior art keywords
- polyimide
- monomer
- constituent
- coverlay
- release layer
- 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.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 167
- 239000004642 Polyimide Substances 0.000 title claims abstract description 99
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 title claims abstract description 13
- 239000013039 cover film Substances 0.000 title abstract 2
- 239000000178 monomer Substances 0.000 claims abstract description 76
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 30
- -1 carbon chain aliphatic diamine Chemical class 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 150000004985 diamines Chemical class 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 19
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 47
- 239000000470 constituent Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 30
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 23
- 238000012545 processing Methods 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000004593 Epoxy Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229920005575 poly(amic acid) Polymers 0.000 claims description 14
- 239000011241 protective layer Substances 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 239000003063 flame retardant Substances 0.000 claims description 5
- 150000003949 imides Chemical class 0.000 claims description 5
- 150000002466 imines Chemical class 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000003822 epoxy resin Substances 0.000 description 20
- 229920000647 polyepoxide Polymers 0.000 description 20
- 238000000576 coating method Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 238000004132 cross linking Methods 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 13
- 239000004342 Benzoyl peroxide Substances 0.000 description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical group O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 9
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 7
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000000539 dimer Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000003466 welding Methods 0.000 description 5
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000009172 bursting Effects 0.000 description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 4
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- TXVWTOBHDDIASC-UHFFFAOYSA-N 1,2-diphenylethene-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)=C(N)C1=CC=CC=C1 TXVWTOBHDDIASC-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- ZXLYUNPVVODNRE-UHFFFAOYSA-N 6-ethenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=C)=N1 ZXLYUNPVVODNRE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- PMAPIPPKZXGDFA-UHFFFAOYSA-N 2-[(2-carboxyanilino)methylamino]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1NCNC1=CC=CC=C1C(O)=O PMAPIPPKZXGDFA-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WQQCEOITPXBDDW-UHFFFAOYSA-N 4-(4-amino-3-methylphenyl)-2-methylaniline Chemical group CC=1C=C(C=CC1N)C1=CC(=C(N)C=C1)C.CC=1C=C(C=CC1N)C1=CC(=C(N)C=C1)C WQQCEOITPXBDDW-UHFFFAOYSA-N 0.000 description 1
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 1
- KXEPRLUGFAULQX-UHFFFAOYSA-N 4-[2,5-di(propan-2-yl)phenyl]aniline Chemical compound CC(C)C1=CC=C(C(C)C)C(C=2C=CC(N)=CC=2)=C1 KXEPRLUGFAULQX-UHFFFAOYSA-N 0.000 description 1
- HESXPOICBNWMPI-UHFFFAOYSA-N 4-[2-[4-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=C(C(C)(C)C=2C=CC(N)=CC=2)C=CC=1C(C)(C)C1=CC=C(N)C=C1 HESXPOICBNWMPI-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 1
- WWEWYHLJEWDHLY-UHFFFAOYSA-N C(=C)C1=C(C(=CC(=C1)N)N)C=CC1=CC=CC=C1 Chemical compound C(=C)C1=C(C(=CC(=C1)N)N)C=CC1=CC=CC=C1 WWEWYHLJEWDHLY-UHFFFAOYSA-N 0.000 description 1
- 241001232787 Epiphragma Species 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- IMYZQPCYWPFTAG-UHFFFAOYSA-N Mecamylamine Chemical compound C1CC2C(C)(C)C(NC)(C)C1C2 IMYZQPCYWPFTAG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- ATJCASULPHYKHT-UHFFFAOYSA-N hexadecane-1,16-diamine Chemical compound NCCCCCCCCCCCCCCCCN ATJCASULPHYKHT-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- CJYCVQJRVSAFKB-UHFFFAOYSA-N octadecane-1,18-diamine Chemical compound NCCCCCCCCCCCCCCCCCCN CJYCVQJRVSAFKB-UHFFFAOYSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Laminated Bodies (AREA)
Abstract
The composition for forming the soluble polyimide comprises a diamine monomer of long carbon chain aliphatic, a monomer containing a group selected from hydroxyl, carboxyl and C ═ C, a tetracarboxylic dianhydride monomer, a bridging agent or an initiator and a solvent. The long carbon chain aliphatic diamine monomer has a main chain having 16 or more carbon atoms. The composition for forming soluble polyimide, the cover film and the manufacturing method thereof provided by the invention can be used for preparing the polyimide film which has the advantages of low dielectric constant, low dielectric loss, low moisture absorption rate, low Young modulus, good chemical resistance and heat resistance and can meet the requirement of thinning.
Description
Technical field
The present invention relates to a kind of constituent, including coverlay and the manufacture thereof of the film prepared by described constituent
Method, particularly relates to a kind of constituent in order to form soluble polyimide, including by described in order to shape
The coverlay of the polyimide film that the constituent of one-tenth soluble polyimide prepares and manufacture method thereof.
Background technology
Along with portable electric product is increasingly towards frivolous trend development, the use demand of flexible circuit board
Amount is also substantially improved.The main upstream materials of flexible circuit board is flexible copper foil substrate, its typically by
Being covered on Copper Foil by coverlay and make, wherein coverlay includes polyimide film.Although industry at present
Used in the thickness of polyimide film the thinnest up to 5 μm, but form the polyimides of this kind of thickness
The processing procedure of film is the most numerous and diverse, causes there is the problem that making is difficult to, cost increases.Additionally, current industry
Used in polyimide film also have that dielectric property is the best, hydroscopicity is high so that in back welding process easily
Occur plate bursting and Young's modulus high so that the strong shortcoming of bounce.Therefore, the most effectively produce the thinnest
The polyimide film that type, dielectric property are good, hydroscopicity is low and Young's modulus is low, actually at present the most urgently gram
One of problem of clothes.
Summary of the invention
The present invention provides a kind of in order to form the constituent of soluble polyimide, coverlay and manufacturer thereof
Method.
The present invention provides a kind of constituent in order to form soluble polyimide, and it can prepare the most slim
Change, the polyimide film that dielectric property is good, hydroscopicity is low, Young's modulus is low and endurance is good, and described
Polyimide film is be applicable to coverlay.
The present invention includes Long carbon chain aliphatic diamidogen list in order to forming the constituent of soluble polyimide
Body, containing selected from the monomer of group of hydroxyl, carboxyl and C=C, tetracarboxylic dianhydride's monomer, bridging agent or
Initiator and solvent.The carbon number of the main chain of the aliphatic diamine monomer of Long carbon chain is more than 16.
In one embodiment of the present invention, the carbon of the main chain of the aliphatic diamine monomer of above-mentioned Long carbon chain
Number is more than 36.
In one embodiment of the present invention, above-mentioned containing the group selected from hydroxyl, carboxyl and C=C
Monomer include choosing freely contain the diamine monomer of hydroxyl, anhydride monomers containing carboxyl, containing the two of carboxyl
At least one in the group that amine monomers and the diamine monomer containing C=C are formed.
In one embodiment of the present invention, above-mentioned bridging agent includes containing epoxy radicals or NCO
Compound, initiator includes peroxide.
In one embodiment of the present invention, above-mentioned solvent includes toluene, dimethylbenzene, hexamethylene, ring
Hexanone, N-Methyl pyrrolidone, dimethyl acetylamide, dimethylformamide or its mixture.
In one embodiment of the present invention, the above-mentioned constituent in order to form soluble polyimide is also
Including additive, described additive includes flame retardant, coloring agent, filler or a combination thereof thing.
The manufacture method of the coverlay of the present invention comprises the following steps.First, make above-mentioned in order to formed can
The constituent of dissolubility polyimides forms the mixed solution containing polyimides.Then, by containing polyimides
Mixed solution is coated on release layer.Then, the coating of the mixed solution containing polyimides is heated
Processing procedure, to form polyimide film on release layer.Afterwards, polyimide film forms following layer.
In one embodiment of the present invention, the method bag of the above-mentioned mixed solution containing polyimides is formed
Include following steps.First, by aliphatic for Long carbon chain diamine monomer, contain selected from hydroxyl, carboxyl and C=C
The monomer of group and tetracarboxylic dianhydride's monomer be dissolved in solvent, and carry out being reacted to form polyamic acid
Solution.Then, carry out polyamic acid solution being cyclized processing procedure, to form polyimide solution.Afterwards,
Bridging agent or initiator are added in polyimide solution.
In one embodiment of the present invention, the process temperatures of above-mentioned heating processing is between 100 DEG C extremely
Between 180 DEG C, the process temperatures of cyclisation processing procedure is between 160 DEG C to 200 DEG C.
In one embodiment of the present invention, the thickness of above-mentioned polyimide film between 1 μm to 20 μm
Between.
In one embodiment of the present invention, above-mentioned release layer is zero diopter or dumb light.
In one embodiment of the present invention, above-mentioned release layer is that one side is release, and above-mentioned coverlay
Manufacture method be additionally included on following layer formation protective layer, described protective layer includes separated type material.
In one embodiment of the present invention, above-mentioned release layer is two-sided release.
The coverlay of the present invention includes release layer, polyimide film and following layer.Polyimide film configures
On release layer, and polyimide film be by above-mentioned in order to forming the constituent of soluble polyimide and
Formed.Following layer is configured on polyimide film.
In one embodiment of the present invention, the thickness of above-mentioned polyimide film between 1 μm to 20 μm
Between.
In one embodiment of the present invention, above-mentioned release layer is zero diopter or dumb light.
In one embodiment of the present invention, above-mentioned release layer is that one side is release, and above-mentioned coverlay
Also including the protective layer being configured on following layer, described protective layer includes separated type material.
In one embodiment of the present invention, above-mentioned release layer is two-sided release.
Based on above-mentioned, include main chain by the present invention in order to forming the constituent of soluble polyimide
The aliphatic diamine monomer of carbon number Long carbon chain more than 16, containing selected from hydroxyl, carboxyl and C=C
The monomer of group, tetracarboxylic dianhydride's monomer, bridging agent or initiator and solvent so that through gathering that it prepares
Acid imide film can have low-k, low-dielectric loss, low hydroscopicity, low Young's modulus, good
Endurance and thermostability, and the requirement of slimming can be reached.
For the features described above of the present invention and advantage can be become apparent, embodiment cited below particularly, and join
Conjunction accompanying drawing is described in detail below.
Accompanying drawing explanation
Fig. 1 is the manufacturing flow chart of the coverlay of an embodiment of the present invention；
Fig. 2 is the schematic diagram of the coverlay of an embodiment of the present invention.
Description of reference numerals:
100: release layer；
102: polyimide film；
104: following layer；
1000: coverlay；
S10, S20, S30, S40: step.
Detailed description of the invention
In this article, " numerical value is to another numerical value " scope represented, is that one is avoided in the description
Enumerate the summary representation of all numerical value in this scope.Therefore, a certain special value scope
Record, contain any number in this numerical range and defined by any number in this numerical range
The relatively fractional value scope gone out, as write out this any number and this relatively fractional value scope in the description in plain text
Equally.
In order to prepare easy slimming, dielectric property is good, hydroscopicity is low, Young's modulus is low and endurance is good
And the polyimide film being suitably applied in coverlay, the present invention proposes a kind of in order to form solubility polyamides
The constituent of imines, can reach above-mentioned advantage by the polyimide film obtained by described constituent.Hereinafter,
The example can actually implemented according to this as the present invention especially exemplified by embodiment.
An embodiment of the present invention provides a kind of constituent in order to form soluble polyimide, and it includes
The aliphatic diamine monomer of Long carbon chain, containing selected from the monomer of group of hydroxyl, carboxyl and C=C, tetracarboxylic acid
Acid dianhydride monomer, bridging agent or initiator and solvent.Hereinafter, above-mentioned various components will be carried out in detail
Explanation.
The carbon number of the main chain of the aliphatic diamine monomer of Long carbon chain is more than 16, preferably more than 36.When
When the carbon number of main chain is less than 16, then too short because of aliphatic chain so that by gathering that described diamine monomer prepares
Acid imide dissolubility is the best, and water absorption and electrical characteristic relatively poor.It addition, in one embodiment,
The carbon number of the main chain of the aliphatic diamine monomer of Long carbon chain is less than 40.
Specifically, the aliphatic diamine monomer of Long carbon chain includes but not limited to: 1,16-hexadecane diamidogen
(1,16-Hexadecane diamine), 1,18-octadecamethylene diamine (1,18-Octadecane diamine).
It addition, be used as commercially available prod as the aliphatic diamine monomer of Long carbon chain, such as PriamineTM 1074
-Dimer diamine or PriamineTM1075 (Japan standing grain big (Croda Japan) company manufacture) or
Versamine 551 (BASF AG's manufacture).
What deserves to be explained is, in the present embodiment, in order to just to form the constituent of soluble polyimide
Being the aliphatic diamine monomer of Long carbon chain more than 16 of the carbon number by employing main chain and reach can
Form the purpose of soluble polyimide.It addition, also lead in order to form the constituent of soluble polyimide
Cross the carbon number the employing main chain aliphatic diamine monomer of Long carbon chain more than 16, and make to prepare through it
Polyimide film can have low-k, low-dielectric loss, low hydroscopicity and low Young mould simultaneously
The character of amount.
Monomer containing the group selected from hydroxyl, carboxyl and C=C includes that choosing freely contains the diamidogen list of hydroxyl
Body, the anhydride monomers containing carboxyl, the diamine monomer containing carboxyl and the diamine monomer institute group containing C=C
At least one in the group become.In one embodiment, containing the base selected from hydroxyl, carboxyl and C=C
The monomer of group such as includes the anhydride monomers containing carboxyl and the diamine monomer containing carboxyl.
Specifically, the diamine monomer containing hydroxyl includes but not limited to: 3,3 '-dihydroxy-4,4 '-diaminourea
Biphenyl (3,3 '-Dihydroxy-4,4 '-diamino-biphenyl are called for short HAB)；Anhydride containing carboxyl
Monomer includes but not limited to: trimellitic anhydride (trimellitic acid anhydride is called for short TMA)；
Diamine monomer containing carboxyl includes but not limited to: 3,5-diaminobenzoic acid (3,5-diaminobenzoic
Acid, be called for short DABZ), 6,6 '-bis-amino-3,3 '-methene base dibenzoic acid (methylene bis (anthranilic
Acid), it is called for short MBAA)；Diamine monomer containing C=C includes but not limited to: 2-vinyl-4,6-
Diaminostilbene, 3,5-triazine (2-vinyl-4,6-diamino-1,3,5-triazine), 2,4-diaminourea-6-(isobutyl
Alkene acyloxy) ethyl-1,3,5-triazine (2,4-diamino-6-(methacryloyloxy) ethyl-1,3,5-
triazine).In one embodiment, the monomer example containing the group selected from hydroxyl, carboxyl and C=C
As included trimellitic anhydride and 3,5-diaminobenzoic acid.
Tetracarboxylic dianhydride's monomer can be the arbitrary tetracarboxylic dianhydride's chemical combination well known to those skilled in the art
Thing.Specifically, tetracarboxylic dianhydride's monomer includes but not limited to: 4, the double phthalic anhydride of 4 '-oxygen
(Bis-(3-phthalyl anhydride) ether, be called for short ODPA), 3,3 ', 4,4 '-benzophenone tetracarboxylic two
Acid anhydride (3,3 ', 4,4 '-Benzophenonetetracarboxylic dianhydride are called for short BTDA), equal benzene four
Formic acid dianhydride (Pyromellitic Dianhydride is called for short PMDA), Bisphenol A Type Diether Dianhydride
(4,4 '-(4,4 '-isopropylidenediphenoxy) bis (phthalic anhydride), be called for short BPADA) or
3,3 ', 4, (3,3 ', 4,4 '-Biphenyltetracarboxylic dianhydride are called for short 4 '-biphenyl tetracarboxylic dianhydride
BPDA).Furthermore, in the present embodiment, aforementioned cited tetracarboxylic dianhydride's monomer can be single
Solely use or be used in mixed way.
Bridging agent includes the compound containing epoxy radicals or NCO.Specifically, bridging agent includes
But it is not limited to: phenol aldehyde type epoxy resin (phenol novolac type epoxy resin), naphthalene type asphalt mixtures modified by epoxy resin
Fat (naphthalene type epoxy resin) or bisphenol A type epoxy resin (bisphenol A type epoxy
resin).It addition, commercially available prod, such as CNE-200EL can be used as the bridging agent containing epoxy radicals
Or PNE-177 (manufacture of CCP Changchun company), EPOXY 4700 (manufacture of DIC company) or
ESCV-90CR (manufacture of chemical company of Nippon Steel)；And can as the bridging agent containing NCO
Use commercially available prod, such as Desmodur N 3600 or Desmodur VK10 (manufacture of Bayer company).
Initiator includes peroxide.Specifically, initiator includes but not limited to: benzoyl peroxide (benzoyl
Peroxide, is called for short BPO), tertbutanol peroxide (tert-Butyl hydroperoxide, be called for short TBH)
Or the double lauroyl (Dilauroyl peroxide) of peroxidating.
It is noted that bridging agent can enter with the hydroxyl in the monomer containing hydroxyl or carboxyl or carboxyl
Row cross-linking reaction, and initiator can assist in the C=C in the monomer containing C=C and carries out cross-linking reaction.
If it is to say, employing the list containing hydroxyl or carboxyl in order to form the constituent of soluble polyimide
Body, then select to use bridging agent；And if in order to formed the constituent of soluble polyimide employ containing
The monomer of C=C, then select to use initiator.Consequently, it is possible in order to the group forming soluble polyimide
Become thing by including monomer containing the group selected from hydroxyl, carboxyl and C=C and bridging agent or initiator,
Make can have good endurance and thermostability through its polyimide film prepared.
Solvent includes but not limited to: toluene, dimethylbenzene, hexamethylene, Ketohexamethylene, N-Methyl pyrrolidone,
Dimethyl acetylamide, dimethylformamide or its mixture.In one embodiment, solvent e.g. ring
Hexanone and the mixture of N-Methyl pyrrolidone.
It addition, the diamidogen that can also include other in order to form the constituent of soluble polyimide of the present invention
Monomer, such as 2,2 '-bis-[4-(4-aminophenoxy phenyl)] propane (2,2 '-Bis
[4-(4-aminophenoxy) phenyl] propane, be called for short BAPP), 4,4 '-MDA
(4,4 '-Methylene dianiline), α, α '-two (4-aminophenyl)-1,4-diisopropyl benzene
(α, α '-bis (4-aminophenyl)-1,4-diisopropylbenzene), 4,4 '-diaminodiphenyl ether
(4,4 '-Oxydianiline), 3,3 '-dimethyl-4,4 '-benzidine
(3,3 '-Dimethyl-4,4 '-diaminobiphenyl) or double (4-amino-benzene oxygen) benzene (1,4-Bis of 1,4-
(4-aminophenoxy)benzene)。
It addition, at the effective scope of the constituent in order to form soluble polyimide not undermining the present invention
In, can be according to need possibly together with additive in order to form the constituent of soluble polyimide.Described additive
Including flame retardant, coloring agent, filler or a combination thereof thing.
Flame retardant includes but not limited to: organophosphor based compound, organic nitrogen based compound, or inorganic hydrogen-oxygen
Change aluminum.Specifically, in order to form the constituent of soluble polyimide by including flame retardant so that
Good flame resistance can be had through its polyimide film prepared.
Coloring agent includes but not limited to: pigment, dyestuff, carbon dust or titanium dioxide.Specifically, in order to
Form the constituent of soluble polyimide by including coloring agent, enabling adjust through gathering that it prepares
The color of acid imide film.
Filler includes but not limited to: silicon dioxide or calcium carbonate.Specifically, in order to form solubility
The constituent of polyimides is by including filler so that can have good through its polyimide film prepared
Good hardness and wearability.
Further, since the present invention's can form solubility in order to forming the constituent of soluble polyimide
Polyimides, therefore applied the polyimide film in forming coverlay so that described coverlay can
Reach the demand of slimming.Hereinafter, will be described in detail with reference to Fig. 1 and Fig. 2.
Fig. 1 is the manufacturing flow chart of the coverlay of an embodiment of the present invention.Fig. 2 is the present invention one enforcement
The schematic diagram of the coverlay of mode.And in fig. 2, each layer is not drawn to scale.
Refer to Fig. 1, carry out step S10, make in any one aforementioned embodiments in order to form solubility
The constituent of polyimides forms the mixed solution containing polyimides.Specifically, formed containing polyimides
The method of mixed solution comprise the following steps.First, by aliphatic for Long carbon chain diamine monomer, contain
The monomer of group and tetracarboxylic dianhydride's monomer selected from hydroxyl, carboxyl and C=C are dissolved in solvent, go forward side by side
Row is reacted to form polyamic acid solution.In one embodiment, in abovementioned steps, response time example
In this way between 1 hour to 6 hour；And the solid content of polyamic acid solution is e.g. between 10%
Between 50%, but the present invention is not limited to this.
Then, carry out polyamic acid solution being cyclized processing procedure, to form polyimide solution.In described step
In Zhou, the process temperatures of cyclisation processing procedure is e.g. between 160 DEG C to 200 DEG C；Processing time is such as
It is between 1 hour to 6 hour；And the solid content of polyimide solution e.g. between 10% to
Between 50%.Specifically, in cyclisation processing procedure, it is (the most de-that polyamic acid can carry out imidization reaction
Water cyclization) and formed and dissolve in the polyimides in solvent, i.e. polyimide solution.In more detail and
Speech, as it was noted above, be the carbon by employing main chain in order to form the constituent of soluble polyimide
The number aliphatic diamine monomer of Long carbon chain more than 16, and reach and can form soluble polyimide
Purpose.
Afterwards, bridging agent or initiator are added in polyimide solution, to form mixing containing polyimides
Close solution.Specifically, as it was noted above, according in order to be formed in the constituent of soluble polyimide
The kind of the monomer containing the group selected from hydroxyl, carboxyl and C=C used, in one embodiment,
Mixed solution containing polyimides can include soluble polyimide, solvent and bridging agent；And it is real at another
Executing in mode, the mixed solution containing polyimides can include soluble polyimide, solvent and initiator.
Then, referring to Fig. 1 and Fig. 2, step S20 is carried out, by the mixed solution containing polyimides
Coat on release layer 100, to form a coating (not shown) on release layer 100.In this step
In, coating method includes but not limited to: scraper type coating, the coating of bar formula or screen painting.It addition,
Release layer 100 e.g. can provide enough support forces with the polyimide film for being formed in subsequent step
Mould release membrance realize.It addition, release layer 100 can be zero diopter or dumb light, use adjustment subsequent step
The surface roughness of the polyimide film of middle formation and glossiness.It addition, release layer 100 is two-sided release.
Then, carry out step 30, the coating of the mixed solution containing polyimides is carried out heating processing, with
Release layer 100 is formed polyimide film 102.In one embodiment, in described step, add
The process temperatures of hot processing procedure is e.g. between 100 DEG C to 180 DEG C；Processing time is e.g. between 1
Hour between 6 hours；And the thickness of polyimide film 102 e.g. between 1 μm to 20 μm it
Between.In another embodiment, in described step, the process temperatures of heating processing is e.g. between 100 DEG C
Between 180 DEG C；Processing time is e.g. between 1 minute to 20 minute；And polyimide film
The thickness of 102 is e.g. between 1 μm to 20 μm.Specifically, in heating processing, containing poly-
Solvent in imido mixed solution can be removed, and simultaneously containing polyimides mixed solution in can
Dissolubility polyimides and bridging agent can carry out in cross-linking reaction, or the mixed solution containing polyimides can
Dissolubility polyimides can be risen by initiator and at first carry out cross-linking reaction.More specifically, as it was noted above,
By employing the carbon number of main chain long carbon more than 16 in order to forming the constituent of soluble polyimide
The diamine monomer of chain fatty race so that polyimide film 102 can have low-k, low Jie simultaneously
Electrical loss, low hydroscopicity and the character of low Young's modulus；And by order to form soluble polyimide
Constituent employ the monomer containing the group selected from hydroxyl, carboxyl and C=C and bridging agent or initial
Agent so that polyimide film 102 can have good endurance and thermostability.But, the present invention is also
It is not limited to this.In other embodiments, in heating processing, the mixing containing polyimides only can occur
Solvent in solution is removed.
Other one is mentioned that, due to polyimide film 102 be by use coating method and be formed at from
The mixed solution containing polyimides on type layer 100 is formed after carrying out heating processing, therefore polyimide film
The thickness of 102 can control between 1 μm to 20 μm, and effectively achieves the demand of slimming.Enter
For one step, when the thickness of polyimide film 102 is the thinnest, then the mixing containing polyimides that coating is used
The amount closing solution is the fewest, and thereby cost is minimized.
Afterwards, carry out step 40, polyimide film 102 is formed following layer 104, thus completes to cover
The making of epiphragma 1000.The method forming following layer 104 on polyimide film 102 includes by coating
Solid is coated on polyimide film 102 by processing procedure, and wherein said coating process includes but not limited to:
Scraper type coating, bar formula are coated with or screen painting, and solid includes but not limited to: epoxy resin
Solid, acryl resin solid or polyurethane resin solid.It addition, the thickness of following layer 104
Between 5 μm to 50 μm.It addition, in the present embodiment, owing to release layer 100 is two-sided
Release, therefore coverlay 1000 can directly carry out rolling.
It addition, after by carrying out all above step (S10～S40), can be prepared by the present invention one enforcement
The coverlay 1000 of mode.Referring once again to Fig. 2, coverlay 1000 includes release layer 100, is arranged in
Polyimide film 102 on release layer 100 and the following layer 104 being arranged on polyimide film 102.
And about release layer 100, polyimide film 102 and the material of following layer 104, characteristic, formation side
Method and effect etc. the most at large illustrate, therefore do not repeat them here.
What deserves to be explained is, in coverlay 1000, it is configured with polyimide film 102 and then
The release layer 100 of layer 104 can be considered a supporter, thereby makes when using coverlay 1000, polyamides
The size of imines film 102 and following layer 104 is unlikely to deform, and has good dimensional stability.Separately
Outward, as it was noted above, owing to the Young's modulus of polyimide film 102 is low, therefore use upper coverlay 1000
Can have good operability.In one embodiment, coverlay 1000 can be by following layer 104
It is attached on Copper Foil and forms a flexible copper foil substrate.
Furthermore, when coverlay 1000 is applied in flexible copper foil substrate, due to polyimide film
102 have low-k, low-dielectric loss, endurance and thermostability, therefore flexible copper foil substrate can
Have good reliability and process rate.Specifically, to have low dielectric normal for polyimide film 102
Number and low-dielectric loss, thereby make the electricity between circuit in the flexible circuit board that flexible copper foil substrate makes
Property interference reduce, help avoid generation parasitic capacitance and derivative power termination thereof, and avoid signal to prolong
Late or interference and cause power consumption to rise.It addition, when coverlay 1000 is applied in flexible copper foil substrate,
Owing to polyimide film 102 has agent of low hygroscopicity, therefore compared with existing coverlay, coverlay 1000 exists
Another baking processing procedure can not be carried out before back welding process and still make will not occur plate bursting in back welding process,
And then reach minimizing fabrication steps, reduce manufacturing cost and the advantage improving process rate.
It addition, in the embodiment of Fig. 1 and Fig. 2, the release layer 100 in coverlay 1000 is two-sided
Release, but the present invention is not limited to this.In other embodiments, the release layer in coverlay 1000
100 can also be that one side is release.Now, coverlay 1000 also includes being arranged on following layer 104 use
To protect the protective layer (not shown) of following layer 104, and described protective layer includes separated type material.In detail
For, protective layer e.g. mould release membrance or release paper.
Below in reference to embodiment 1～4 and comparative example 1,2, inventive feature more particularly described below.Though
So describe example 1 below～4, but in the case of insurmountability scope, can suitably change
Become material therefor, its amount and ratio, process details and handling process etc..Therefore, should be by not hereafter
Restricting property of the present invention is explained by described embodiment.
Preparation embodiment 1～4 and the main material that used of the polyimides of comparative example 1,2 and coverlay and
The information of equipment is as follows.
The aliphatic diamine monomer of Long carbon chain:
Trade name PriamineTM1074-Dimer diamine, standing grain major company of Japan manufactures, Qi Zhongzhu
The carbon number of chain is 36.
Monomer containing the group selected from hydroxyl, carboxyl and C=C:
Trimellitic anhydride (hereinafter referred to as TMA), purchased from company of Eastcom；
3,5-diaminobenzoic acids (hereinafter referred to as DABZ), purchased from Jin Yu company；
2-vinyl-4,6-diamino-1,3,5-triazines, it is melted into company purchased from four countries.
Tetracarboxylic dianhydride's monomer:
4, the double phthalic anhydride (hereinafter referred to as ODPA) of 4 '-oxygen, purchased from TCI company.
Other diamine monomer:
2,2 '-bis-[4-(4-aminophenoxy phenyl)] propane (hereinafter referred to as BAPP), purchased from company of Eastcom.
Bridging agent:
Trade name EPOXY 4700, DIC company manufactures.
Initiator:
Benzoyl peroxide (hereinafter referred to as BPO), is shown in glad industry manufacture.
Solvent:
Ketohexamethylene, purchased from victory one chemical company；
N-Methyl pyrrolidone (hereinafter referred to as NMP), purchased from Bo Lv company.
Copper Foil: purchased from Japan's electrolysis company.
Polyimide film:
Trade name 30EN, purchased from Du Pont (DuPont) company.
Mould release membrance:
Trade name PET-50-SHP-A, purchased from Fujiko company.
Solid:
Epoxy resin solid, Tai Hong company manufactures.
Low mensuration force detector: manufactured by three rich u s companys (Mitutoyo America Corporation),
Equipment entitled Litematic LV-50A.
Experiment 1
Hereinafter, describe, by embodiment 1 and comparative example 1, the polyamides that aforementioned embodiments is proposed in detail
The characteristic of imines film.
Embodiment 1
Priamine by TMA, 3mol of ODPA, 1.2mol of 4molTM 1074-Dimer
The BAPP of DABZ and 0.5mol of diamine, 1.5mol is dissolved in the mixture of Ketohexamethylene and NMP
In.Then carry out reacting 2 hours by the mixed solution of gained, to obtain the polyamide that solid content is 40%
Acid solution.Then, described polyamic acid solution is carried out imidization reaction 3 hours at 180 DEG C,
To obtain the polyimide solution that solid content is 44%.Then, the EPOXY 4700 of 0.3mol is added
Enter in described polyimide solution, to form the mixed solution containing polyimides.Afterwards, by described containing poly-
Imido mixed solution with scraper for coating on Copper Foil, and then at 160 DEG C heat 2 hours, with
Remove Ketohexamethylene and NMP, and make polyimides and EPOXY 4700 carry out cross-linking reaction.Then,
By etch process, Copper Foil is removed, to obtain the polyimide film of embodiment 1, wherein with low mensuration power
Analyzer carries out the measurement of thickness, and thickness is 7 μm.
Embodiment 2
Priamine by TMA, 3mol of ODPA, 1.2mol of 4molTM 1074-Dimer
2-vinyl-4,6-the diaminostilbene of diamine, 1.5mol, the BAPP of 3,5-triazine and 0.5mol is dissolved in
In the mixture of Ketohexamethylene, NMP and toluene.Then carry out reacting 2 hours by the mixed solution of gained,
To obtain the polyamic acid solution that solid content is 40%.Then, by described polyamic acid solution at 170 DEG C
Under carry out imidization reaction 2 hours, to obtain the polyimide solution that solid content is 42%.Then,
By the EPOXY 4700 of 0.3mol and relative to the weight of described polyimides, addition is 5wt%
BPO add in described polyimide solution, to form the mixed solution containing polyimides.Afterwards, will
The described mixed solution containing polyimides with scraper for coating on Copper Foil, and then at 160 DEG C heat 2
Hour, to remove Ketohexamethylene, NMP and toluene, and make polyimides hand over EPOXY 4700
Connection reacts and makes polyimides be risen by BPO and at first carries out cross-linking reaction.Then, by etch process by copper
Paper tinsel removes, and to obtain the polyimide film of embodiment 2, wherein carries out thickness with low mensuration force detector
Measuring, thickness is 7 μm.
Comparative example 1
As different from Example 1, comparative example 1 prepared polyimide film the most voluntarily, but directly
Connect use commercially available prod polyimide film 30EN (thickness is 7 μm).
Afterwards, respectively the polyimide film of embodiment 1, embodiment 2 and comparative example 1 is carried out Young mould
The mensuration of amount, dielectric constant, dielectric loss and hydroscopicity.Being described as follows of aforementioned each test, and test
Result be shown in table 1.
The mensuration of Young's modulus
The poly-of embodiment 1, embodiment 2 and comparative example 1 is measured according to the regulation of ASTM-D882-02
The Young's modulus of acid imide film.In Table 1, the rigidity of numerical value the lowest expression polyimide film is the least.
Dielectric constant, the mensuration of dielectric loss
The regulation of foundation IPC-TM-6502.5.5.5.1B, use Network Analyzer (model is ZVB20,
Manufactured by Luo De Morrie Schwartz company (ROHDE&SCHWARZ)) measure embodiment 1 respectively, implement
The dielectric constant of the polyimide film of example 2 and comparative example 1 and dielectric loss, wherein measuring frequency is 10
GHz.In Table 1, the dielectric property of numerical value the lowest expression polyimide film is the best.
The mensuration of hydroscopicity
Embodiment 1, embodiment 2 and comparative example 1 is measured according to the regulation of IPC-TM-6502.6.2.1
The hydroscopicity of polyimide film.In Table 1, the hydroscopicity of numerical value the lowest expression polyimide film is the lowest.
Table 1
| Embodiment 1 | Embodiment 2 | Comparative example 1 | |
| Young's modulus (GPa) | 0.9 | 1.81 | 5.0 |
| Dielectric constant | 2.79 | 3.29 | 3.55 |
| Dielectric loss | 0.0064 | 0.0086 | 0.0149 |
| Hydroscopicity (%) | 0.9 | 1.3 | 2.6 |
As shown in Table 1, compared with the polyimide film of comparative example 1 (i.e. commercially available prod), the present invention's
By including the carbon number of the main chain aliphatic diamine monomer of Long carbon chain more than 16, containing selected from hydroxyl, carboxylic
The monomer of the group of base and C=C, tetracarboxylic dianhydride's monomer, bridging agent or initiator and the constituent of solvent
Obtained embodiment 1 and the polyimide film of embodiment 2 have relatively low Young's modulus, dielectric simultaneously
Constant, dielectric loss and hydroscopicity.
Experiment 2
Hereinafter, aforementioned embodiments institute is described in detail by embodiment 3, embodiment 4 and comparative example 2
The characteristic of the coverlay proposed.
Embodiment 3
Priamine by TMA, 3mol of ODPA, 1.2mol of 4molTM 1074-Dimer
The BAPP of DABZ and 0.5mol of diamine, 1.5mol is dissolved in the mixture of Ketohexamethylene and NMP
In.Then carry out reacting 2 hours by the mixed solution of gained, to obtain the polyamide that solid content is 40%
Acid solution.Then, described polyamic acid solution is carried out imidization reaction 3 hours at 180 DEG C,
To obtain the polyimide solution that solid content is 44%.Then, the EPOXY 4700 of 0.3mol is added
Enter in described polyimide solution, to form the mixed solution containing polyimides.Afterwards, by described containing poly-
Imido mixed solution with scraper for coating on mould release membrance PET-50-SHP-A, and then at 160 DEG C
Lower heating 3 minutes, to remove Ketohexamethylene and NMP, and then obtains the polyimide film of embodiment 3.Connect
, by epoxy resin solid with scraper for coating on the polyimide film of embodiment 3, and then exist
Toast 3 minutes at 160 DEG C, to remove the solvent of epoxy resin solid, to obtain the covering of embodiment 3
Film.
Embodiment 4
Priamine by TMA, 3mol of ODPA, 1.2mol of 4molTM 1074-Dimer
2-vinyl-4,6-the diaminostilbene of diamine, 1.5mol, the BAPP of 3,5-triazine and 0.5mol is dissolved in
In the mixture of Ketohexamethylene, NMP and toluene.Then carry out reacting 2 hours by the mixed solution of gained,
To obtain the polyamic acid solution that solid content is 40%.Then, by described polyamic acid solution at 170 DEG C
Under carry out imidization reaction 2 hours, to obtain the polyimide solution that solid content is 42%.Then,
By the EPOXY 4700 of 0.3mol and relative to the weight of described polyimides, addition is 5wt%
BPO add in described polyimide solution, to form the mixed solution containing polyimides.Afterwards, will
The described mixed solution containing polyimides with scraper for coating on mould release membrance PET-50-SHP-A, and then
Heat 3 minutes at 160 DEG C, to remove Ketohexamethylene, NMP and toluene, and then obtain embodiment 4
Polyimide film.Then, by epoxy resin solid with scraper for coating in the polyimide film of embodiment 4
On, and then toast 3 minutes at 160 DEG C, to remove the solvent of epoxy resin solid, to obtain
The coverlay of embodiment 4.
Comparative example 2
In comparative example 2, coverlay be by directly by epoxy resin solid with scraper for coating in commercially available
On product polyimide film 30EN (thickness is 7 μm), and then toast 3 minutes at 160 DEG C,
Obtain to remove the solvent of epoxy resin solid.
Afterwards, coverlay to embodiment 3, embodiment 4 and comparative example 2 carries out the half heat-resisting survey in field respectively
Examination and bounce test.Being described as follows of aforementioned each test, and test result be shown in table 2.
The half resistance to Thermal test in field
Preparation embodiment 3, embodiment 4 and the anti-welding test sheet of comparative example 2: at 190 DEG C, will be real
Execute after the coverlay of example 3, embodiment 4 and comparative example 2 fits on Copper Foil respectively, add at 160 DEG C
Heat 2 hours, so that the polyimides in the coverlay of embodiment 3 and EPOXY 4700 carry out crosslinking instead
And cross-linking reaction should be carried out with epoxy resin solid；Make polyimides in the coverlay of embodiment 4 with
EPOXY 4700 carries out cross-linking reaction and epoxy resin solid carries out cross-linking reaction, and by BPO
Rise and at first carry out cross-linking reaction；And make the epoxy resin solid in the coverlay of comparative example 2 hand over
Connection reaction.
Then, according to the regulation of IPC-TM-650No.2.4.13, respectively to embodiment 3, embodiment 4
And the anti-welding test sheet of comparative example 2 carries out the half resistance to Thermal test in field.In table 2, the highest expression of Temperature numerical
In the case of there is not plate bursting, the temperature that coverlay can bear is the highest.
Bounce is tested
Preparation embodiment 3, the bounce test sheet of embodiment 4 and comparative example 2: first, by embodiment 3,
The coverlay of embodiment 4 and comparative example 2 cuts into length and width a size of 10mm × 30mm respectively.Then,
The coverlay of embodiment 3, embodiment 4 and comparative example 2 after cutting is respectively placed to following layer upward
After, heat 2 hours at 160 DEG C, so that the polyimides in the coverlay of embodiment 3 and EPOXY
4700 carry out cross-linking reaction and carry out cross-linking reaction with epoxy resin solid；Make the coverlay of embodiment 4
In polyimides and EPOXY 4700 carry out cross-linking reaction and epoxy resin solid to carry out crosslinking anti-
Should, and risen by BPO and at first carry out cross-linking reaction；And make the asphalt mixtures modified by epoxy resin in the coverlay of comparative example 2
Fat solid carries out cross-linking reaction.
Then, use bounce tester (by Shimadzu (SHIMADZU) company manufacture, model:
AUY220), respectively the bounce of embodiment 3, embodiment 4 and comparative example 2 is surveyed according to following steps
Test piece carries out bounce test.First, correction balance is adjusted to zero.Then, respectively by embodiment 3,
One end of the bounce test sheet of embodiment 4 and comparative example 2 is fixed at the holder above test tablet tray,
The other end is then stuck on the deck at test tablet tray center, so that embodiment 3, embodiment 4 and compare
The bounce test bending tablet of example 2 becomes "U" shaped.Afterwards, under making the deck at test tablet tray center slowly
Fall, until it contacts with inferior shim, at the same time, balance reading declines with deck and changes, meter
The maximum recording this variation is bounce-back force value.In table 2, the bounce of numerical value the lowest expression coverlay is more
Low.
Table 2
As shown in Table 2, in the half resistance to Thermal test in field, compared with the coverlay of comparative example 2, the present invention's
The coverlay of embodiment 3 and embodiment 4 still is able in higher temperature (288 DEG C) before toasting
There is not plate bursting down.It addition, as shown in Table 2, compared with the coverlay of comparative example 2, the present invention's
The coverlay of embodiment 3 and embodiment 4 has relatively low bounce.
Last it is noted that various embodiments above is only in order to illustrate technical scheme, rather than right
It limits；Although the present invention being described in detail with reference to foregoing embodiments, this area common
Skilled artisans appreciate that the technical scheme described in foregoing embodiments still can be modified by it,
Or the most some or all of technical characteristic is carried out equivalent；And these amendments or replacement, and
The essence not making appropriate technical solution departs from the scope of various embodiments of the present invention technical scheme.
Claims (20)
1. one kind in order to form the constituent of soluble polyimide, it is characterised in that including:
The aliphatic diamine monomer of Long carbon chain, the main chain of the aliphatic diamine monomer of wherein said Long carbon chain
Carbon number is more than 16；
Monomer containing the group selected from hydroxyl, carboxyl and C=C；
Tetracarboxylic dianhydride's monomer；
Bridging agent or initiator；And
Solvent.
Constituent in order to form soluble polyimide the most according to claim 1, its feature exists
In, the carbon number of the main chain of the aliphatic diamine monomer of described Long carbon chain is more than 36.
Constituent in order to form soluble polyimide the most according to claim 1, its feature exists
In, the described monomer containing the group selected from hydroxyl, carboxyl and C=C includes that choosing freely contains the two of hydroxyl
Amine monomers, the anhydride monomers containing carboxyl, the diamine monomer containing carboxyl and the diamine monomer containing C=C
At least one in the group formed.
Constituent in order to form soluble polyimide the most according to claim 1, its feature exists
In, described bridging agent includes the compound containing epoxy radicals or NCO, and described initiator included
Oxide.
Constituent in order to form soluble polyimide the most according to claim 1, its feature exists
In, described solvent includes toluene, dimethylbenzene, hexamethylene, Ketohexamethylene, N-Methyl pyrrolidone, diformazan
Yl acetamide, dimethylformamide or its mixture.
Constituent in order to form soluble polyimide the most according to claim 1, its feature exists
In, also include that additive, described additive include flame retardant, coloring agent, filler or a combination thereof thing.
7. the manufacture method of a coverlay, it is characterised in that including:
The constituent in order to form soluble polyimide according to claim 1 is made to be formed containing polyamides
The mixed solution of imines；
The described mixed solution containing polyimides is coated on release layer；
The described mixed solution containing polyimides is carried out heating processing, poly-to be formed on described release layer
Acid imide film；And
Described polyimide film is formed following layer.
The manufacture method of coverlay the most according to claim 7, it is characterised in that contain described in formation
The method of the mixed solution of polyimides includes:
By aliphatic for Long carbon chain diamine monomer, containing the monomer of group selected from hydroxyl, carboxyl and C=C
And tetracarboxylic dianhydride's monomer is dissolved in solvent, and carry out being reacted to form polyamic acid solution；
Carry out described polyamic acid solution being cyclized processing procedure, to form polyimide solution；And
Bridging agent or initiator are added in described polyimide solution.
The manufacture method of coverlay the most according to claim 8, it is characterised in that described heating system
The process temperatures of journey is between 100 DEG C to 180 DEG C, and the process temperatures of described cyclisation processing procedure is between 160 DEG C
Between 200 DEG C.
The manufacture method of coverlay the most according to claim 7, it is characterised in that described polyamides
The thickness of imines film is between 1 μm to 20 μm.
The manufacture method of 11. coverlays according to claim 7, it is characterised in that described release
Layer is zero diopter or dumb light.
The manufacture method of 12. coverlays according to claim 7, it is characterised in that described release
Layer is that one side is release.
The manufacture method of 13. coverlays according to claim 12, it is characterised in that be additionally included in
Forming protective layer on described following layer, described protective layer includes separated type material.
The manufacture method of 14. coverlays according to claim 7, it is characterised in that described release
Layer is two-sided release.
15. 1 kinds of coverlays, it is characterised in that including:
Release layer；
Polyimide film, is configured on described release layer, and described polyimide film is by according to claim
Being formed in order to form the constituent of soluble polyimide described in 1；And
Following layer, is configured on described polyimide film.
16. coverlays according to claim 15, it is characterised in that the thickness of described polyimide film
Degree is between 1 μm to 20 μm.
17. coverlays according to claim 15, it is characterised in that described release layer be zero diopter or
Dumb light.
18. coverlays according to claim 15, it is characterised in that described release layer be one side from
Type.
19. coverlays according to claim 18, it is characterised in that also include protective layer, configuration
On described following layer, described protective layer includes separated type material.
20. coverlays according to claim 15, it is characterised in that described release layer be two-sided from
Type.
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| Application Number | Priority Date | Filing Date | Title |
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| TW104116989A TWI557180B (en) | 2015-05-27 | 2015-05-27 | Composition for forming dissolvable polyimide, coverlayer, and manufacturing method thereof |
| TW104116989 | 2015-05-27 |
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| CN106279686A true CN106279686A (en) | 2017-01-04 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117418A (en) * | 2018-02-07 | 2019-08-13 | 台虹科技股份有限公司 | The production method of cover film and the insulating layer of semiconductor component surfaces |
| JP2019172989A (en) * | 2018-03-28 | 2019-10-10 | 荒川化学工業株式会社 | Polyimide, adhesive, crosslinking agent, film-like adhesive, adhesive layer, adhesive sheet, copper foil with resin, copper clad laminate, printed wiring board and multilayer wiring sheet, and manufacturing method therefor |
| TWI757589B (en) * | 2018-06-25 | 2022-03-11 | 亞洲電材股份有限公司 | Ultra-thin and highly transparent polyimide film and the preparation method thereof |
| CN114685787A (en) * | 2020-12-27 | 2022-07-01 | 上海市塑料研究所有限公司 | Polyimide film with synergistic cross-linking structure and preparation method and application thereof |
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| WO2014208644A1 (en) * | 2013-06-28 | 2014-12-31 | 新日鉄住金化学株式会社 | Polyimide, resin film, and metal-clad laminate |
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| CN103289633A (en) * | 2012-02-24 | 2013-09-11 | 荒川化学工业株式会社 | Polyimide-based adhesive composition, cured product, adhesive sheet, laminate, and flexible printed circuit board |
| WO2014208644A1 (en) * | 2013-06-28 | 2014-12-31 | 新日鉄住金化学株式会社 | Polyimide, resin film, and metal-clad laminate |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117418A (en) * | 2018-02-07 | 2019-08-13 | 台虹科技股份有限公司 | The production method of cover film and the insulating layer of semiconductor component surfaces |
| CN110117418B (en) * | 2018-02-07 | 2022-01-28 | 台虹科技股份有限公司 | Method for manufacturing cover film and insulating layer on surface of semiconductor element |
| JP2019172989A (en) * | 2018-03-28 | 2019-10-10 | 荒川化学工業株式会社 | Polyimide, adhesive, crosslinking agent, film-like adhesive, adhesive layer, adhesive sheet, copper foil with resin, copper clad laminate, printed wiring board and multilayer wiring sheet, and manufacturing method therefor |
| JP7205335B2 (en) | 2018-03-28 | 2023-01-17 | 荒川化学工業株式会社 | Polyimide, adhesive, cross-linking agent, film-like adhesive, adhesive layer, adhesive sheet, resin-coated copper foil, copper-clad laminate, printed wiring board, multilayer wiring board, and manufacturing method thereof |
| TWI757589B (en) * | 2018-06-25 | 2022-03-11 | 亞洲電材股份有限公司 | Ultra-thin and highly transparent polyimide film and the preparation method thereof |
| CN114685787A (en) * | 2020-12-27 | 2022-07-01 | 上海市塑料研究所有限公司 | Polyimide film with synergistic cross-linking structure and preparation method and application thereof |
| CN114685787B (en) * | 2020-12-27 | 2024-03-08 | 上海市塑料研究所有限公司 | Polyimide film with synergistic crosslinking structure and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI557180B (en) | 2016-11-11 |
| TW201641597A (en) | 2016-12-01 |
| CN106279686B (en) | 2019-05-07 |
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