CN100494279C - Method for making thermoplastic polyimide combination and two-side soft copper foil substrate - Google Patents
Method for making thermoplastic polyimide combination and two-side soft copper foil substrate Download PDFInfo
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- CN100494279C CN100494279C CNB2006100908426A CN200610090842A CN100494279C CN 100494279 C CN100494279 C CN 100494279C CN B2006100908426 A CNB2006100908426 A CN B2006100908426A CN 200610090842 A CN200610090842 A CN 200610090842A CN 100494279 C CN100494279 C CN 100494279C
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- polyimide
- copper foil
- double
- thermoplastic polyimide
- silane
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000011889 copper foil Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229920006259 thermoplastic polyimide Polymers 0.000 title claims description 55
- 239000000758 substrate Substances 0.000 title claims description 23
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000077 silane Inorganic materials 0.000 claims abstract description 23
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 10
- 229920001721 polyimide Polymers 0.000 claims description 60
- 239000004642 Polyimide Substances 0.000 claims description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- -1 glycidoxy propyl group Chemical group 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims description 2
- 150000002924 oxiranes Chemical group 0.000 claims 7
- 239000000654 additive Substances 0.000 claims 4
- 239000004927 clay Substances 0.000 claims 2
- 239000004593 Epoxy Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 5
- 229920001169 thermoplastic Polymers 0.000 abstract description 3
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 3
- 229920000768 polyamine Polymers 0.000 abstract 6
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000009719 polyimide resin Substances 0.000 description 36
- 239000010410 layer Substances 0.000 description 19
- SECXISVLQFMRJM-UHFFFAOYSA-N N-methyl-pyrrolidinone Natural products CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011888 foil Substances 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 238000000576 coating method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- 150000002118 epoxides Chemical group 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 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 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 101710194411 Triosephosphate isomerase 1 Proteins 0.000 description 3
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 101150033824 PAA1 gene Proteins 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-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
- DXYLECNPBQRBQL-UHFFFAOYSA-N CCC.NC1=CC=C(OC2=CC=C(C=C2)C(C)(C)C2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1 Chemical compound CCC.NC1=CC=C(OC2=CC=C(C=C2)C(C)(C)C2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1 DXYLECNPBQRBQL-UHFFFAOYSA-N 0.000 description 1
- CHEYZUXMKGVAHL-UHFFFAOYSA-N CO[Si](CCC1CC2OC2CC1)(OC)OC.C(C)[Si](OC)(OC)OC Chemical compound CO[Si](CCC1CC2OC2CC1)(OC)OC.C(C)[Si](OC)(OC)OC CHEYZUXMKGVAHL-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910016847 F2-WS Inorganic materials 0.000 description 1
- 101710174876 Probable triosephosphate isomerase 2 Proteins 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
- 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 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- HUUCHDRSMXGHFR-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane diethoxy(methyl)silane Chemical compound CCO[SiH](C)OCC.CCO[Si](C)(CCCOCC1CO1)OCC HUUCHDRSMXGHFR-UHFFFAOYSA-N 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
The invention discloses a thermoplastic polyamine composition, which comprises the following parts: (A)silane modified polyamine and (B)polarity agent, wherein the (A)silane modified polyamine is reacted by (a)polyamine and (b)silane with epoxy radical; the (a)polyamine is constituted by repeated units of formula I and formula II with molar piece-rate of the repeated unit of formula II at 10% at least; X is quadrivalent aromatic radical; Ar1 is bivalent aromatic radical; Ar2 is bivalent aromatic radical with COOH or OH. The invention also provides the making method of double-face flexible copper foil base through the thermoplastic polyamine.
Description
Technical field
The present invention relates to a kind of thermoplastic polyimide material, and particularly relate to a kind of thermoplastic polyimide (polyimide of high heat-resisting, high dimensional stability; PI) composition is particularly suitable for being applied in the then making of formulation double-surface flexible copper foil substrate of nothing.
Background technology
Trend in response to compact electronic product, flexible circuit base board structure packing technique also advances towards the target of high-density, graph thinning, considering under the multi-functional and more frivolous situation, the dual platen distribution is best selection, the dual platen of tradition contains solid, and solid is generally epoxy or acryl series, and its thermotolerance and dimensional stability are relatively poor, therefore, the thermoplastic polyimide for the requirement exploitation double-sided metal foil layer laminated board that reaches market is inevitable.
The production method of double-sided metal foil layer laminated board has a variety of, and the direct mode with Copper Foil pressing up and down (lamination) of three strata imide resins is one of them in the middle of utilizing, we can divide according to the technology of middle three strata imide resin layer materials again, and the thermoplastic polyimide resin of heat resistant poly imide resin (PI) and levels is followed material (TPI; Thermoplastic PI) two kinds of materials simultaneously or two kinds of the dual modes of not formations simultaneously, first kind is JP2004042579, JP2003071982, JP2002240195, the US6379784 etc. that the patent of three coatings (TPI/PI/TPI) while coating method comprises Ube.This mode must possess three layers of coating technique are arranged, comprise that the design of dispense tip and the rerum natura between coating or fluid properties all can have influence on the quality of coating, than being easier to apparent problem, also must be noted that baking condition (＜200 ℃) control of the semi-harden state of its interlayer on the other hand, because to then having direct influence.Another kind of coating process is directly at thermotolerance polyimide resin layer (PI base material or basal plate) both sides coating thermoplastic polyimide resin layer, and wherein heat resistant poly imide resin (PI base material) is as kapton E, Apical NPI etc.
The surperficial untreated words property followed of general PI film is very poor, must do surperficial modification to improve following between heat resistant poly imide resin and the thermoplastic polyimide resin.The method of surface modification comprises: the electricity slurry is handled or coating aminosilane couplant modes such as (aminosilane coupling agent), as patent JP11277699, JP08230103 etc. except that the surface modification mode, also can directly remake modification from thermoplastic polyimide resin interpolation silane or epoxy group(ing), utilizing the mode such as the patent JP2003200527 of silane is polyamic acid (polyamic acid) or the carboxylic acid group partly of the not endless loop in the polyimide and organoalkoxysilane (alkoxysilane) reaction that has epoxy group(ing) who utilizes not cyclisation, wherein the silane that is added can not be too high, otherwise film can be crisp, selected monomer structure also can not be soft excessively, otherwise its thermal expansivity (CTE) can be too high, has the problem of dimensional stability and warpage.
The way of another modification is to utilize the epoxy group(ing) modification, is Polyimidesiloxane (the polyimide siloxane that utilizes cyclisation (cyclisation rate〉90%) as patent JP10000733; Its diamine monomer has OH or COOH functional group) add aromatic ring oxygen compound (aromatic epoxy) and mix after, this thermoplastic polyimide is coated in PI base material both sides, form two-sided Copper Foil basal plate with the Copper Foil pressing.The tempering that this method needs to continue for some time after pressing (160 ℃ tempering 1 hour) makes COOH on the PI or OH and epoxy reaction increase then property, has therefore caused technology cost and the increase of time.
Summary of the invention
One of purpose of the present invention just provides a kind of thermoplastic polyimide combination, has advantages such as then high and anti-scolding tin after itself and the Copper Foil pressing.
Two of purpose of the present invention just provides a kind of making method of double-surface flexible copper foil substrate, does not need to carry out back segment cyclisation temperature with high temperature again, can save double-sided metal foil layer laminated board technology cost and time.
For reaching above-mentioned and other purpose, thermoplastic polyimide combination of the present invention comprises: (A) silane-modified polyimide; And (B) polar solvent, wherein (A) silane-modified polyimide is (a) polyimide and the silane reaction gained that (b) has epoxide group, (a) polyimide is made of following formula I and formula II repeating unit, and the mole fraction at least 10% of formula II repeating unit, wherein X is the tetravalence aromatic base; Ar
1Be the divalence aromatic base; Ar
2For containing the divalence aromatic base of carboxylic acid group (COOH) or hydroxyl (OH).
Formula I formula II
The making method of the present invention's double-surface flexible copper foil substrate comprises: the solution that contains aforementioned polyimide (a) is provided; Silane and the reaction of this polyimide to have epoxide group in above-mentioned solution form silane-modified thermoplastic polyimide; Thermoplastic polyimide after the above-mentioned modification is coated the both sides of polyimide basal plate; And, will be coated with basal plate and two Copper Foil hot pressings of thermoplastic polyimide, form double-surface flexible copper foil substrate.
State with other purpose, feature and advantage and can become apparent on the present invention for allowing, cited below particularlyly go out preferred embodiment, and cooperate appended graphicly, be described in detail below:
Description of drawings
Fig. 1 illustrates the making method of double-surface flexible copper foil substrate of the present invention.
The primary clustering nomenclature
100～PI basal plate
110～thermoplastic polyimide combination of the present invention
120～Copper Foil
Embodiment
The present invention system provides a kind of thermoplastic polyimide combination, the then material that can be used for double-sided metal foil layer laminated board, its function is when the double-sided metal foil layer laminated board material is made pressing (lamination), can make to reach between Copper Foil and the thermotolerance polyimide resin layer well then, on the characteristic of double-sided metal foil layer laminated board, reach better thermotolerance and dimensional stability.
Thermoplastic polyimide combination of the present invention mainly comprises: (A) silane-modified polyimide and (B) polar solvent, wherein (A) silane-modified polyimide is to be got with (b) having the silane reaction of epoxide group by (a) polyimide.
Above-mentioned (a) polyimide is the multipolymer of formula I and formula II repeating unit, and the shared mole fraction at least 10% of its Chinese style II repeating unit is preferable between 30%～60%.
Wherein X is the tetravalence aromatic base, and the preferably includes, but is not limited to:
Ar
1Be the divalence aromatic base, the preferably includes, but is not limited to:
Ar
2For containing the divalence aromatic base of carboxylic acid group (COOH) or hydroxyl (OH), the preferably includes, but is not limited to:
According to the present invention, (A) silane-modified polyimide is to utilize its side chain of (a) polyimide (Ar
2) carboxylic acid group (COOH) of part or the silane reaction that hydroxyl (OH) comes to have with (b) epoxide group, wherein (b) silane of having an epoxide group is preferably the oxirane TMOS (non-aromatic epoxyalkoxysilane) of non-aromatic, for example: epoxycyclohexyl organoalkoxysilane (epoxycyclohexyl alkoxysilane), glycidoxy propyl group organoalkoxysilane (glycidoxypropyl alkoxysilane) etc., concrete example comprise (as shown in the formula): β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane (β-(3,4-epoxycyclohexyl) ethyltrimethoxysilane), γ-glycidoxypropyltrime,hoxysilane (γ-glycidoxypropyl-trimethoxysilane), γ-glycidoxy propyl group methyldiethoxysilane (γ-glycidoxypropyl-methyldiethoxysilane) etc.In preferred embodiment of the present invention, (A) the about 15-30 weight of the solid content of silane-modified polyimide %.
Be applicable to that (B) of the present invention polar solvent comprises: N-N-methyl-2-2-pyrrolidone N-(N-methyl-2-pyrrolidone; NMP), N,N-dimethylacetamide (N, N-dimethylacetamide; DMAc), gamma-butyrolactone (γ-butyrolactone; GBL), dimethylbenzene (Xylene), toluene (Toluene), etc. or aforesaid combination, but be not to exceed with above-mentioned solvent, those skilled in the art are when the solvent that can use any suitable polyimide.
The synthesis step of polyimide is for being dissolved in an amount of diamine monomer and dicarboxylic anhydride monomer in the appropriate solvent (as NMP etc.), and after stirred for several hour, add azeotropic solvent (as toluene) and be heated to about 180 ℃ and make its backflow, with its cooling, the content of polyimide is preferable in the solution is controlled at about 15-30 weight % after about 1～3 hour.Then, add an amount of silane that has epoxide group and catalyzer (as TPP; Triphenylphosphine (triphenylphosphine)) reacted 3～5 hours down in 90～160 ℃ (preferable 100～130 ℃), can obtain thermoplastic polyimide resin (TPI).During reaction, having the preferable molar ratio of the silane of epoxide group and polyimide is 1:1～1:3.
Thermoplastic polyimide of the present invention, its limiting viscosity (I.V.; Intrinsic Viscosity), preferable between 0.6～0.8 more preferably greater than 0.5dl/g.Its weight average molecular weight generally can be in 10000～100000 scope, but with preferable between 20000～60000.
In addition, for considering that the Copper Foil etching warpage issues may occur after intact, can in thermoplastic polyimide resin, add the small amounts of inorganic powder in case of necessity and improve, as other inorganicss such as silicon-dioxide, lime carbonate, talcum powder or clays to reduce its thermal expansivity effect.Wherein the preferable addition of inorganic powder is 0.1～5 weight % (the solid composition with PI is a benchmark).
The 1st figure shows the application of thermoplastic polyimide of the present invention in double-surface flexible copper foil substrate.At first, (PI base material, both sides NPI) after 120 ℃～250 ℃ baking, are controlled between 3～6 μ m coating thickness thermoplastic polyimide 110 of the present invention to be coated on heat resistant poly imide resin basal plate 100.Utilize the hot pressing mode to form double-sided metal foil layer laminated board Copper Foil 120 and thermoplastic polyimide 110 more at last, its temperature, pressure is preferably 320～350 ℃, 50～80Kg/cm
2, (preferable about 5～20 minutes) can finish in 30 minutes.
It should be noted, because thermoplastic polyimide of the present invention is to have finished modified-reaction at synthesis phase (in solution), therefore the thermoplastic polyimide 110 that is coated on the PI base material 100 itself just has good then character, in follow-up process for pressing, do not need to carry out back segment thermal treatment with high temperature again and just can reach well then, therefore can save double-sided metal foil layer laminated board technology cost and time.In addition, obtained double-sided metal foil layer laminated board has better thermotolerance and dimensional stability, can reach the target of the densification graph thinning of structure packing technique.
Embodiment
Medicine
ODPA:4,4 '-oxydiphthalic anhydride (4,4 '-oxydiphthalic anhydride)
BPADA:4,4 '-dihydroxyphenyl propane dianhydride (4,4 '-Bisphenol A Dianhydride)
DABZ:3,5-diaminobenzoic acid (3,5-diaminobenzoic acid)
MBAA: methylene-bis (anthranilic acid) (Methylene Bis (anthranilic acid))
M-BAPS:4,4 '-two (3-amino-benzene oxygen) sulfobenzide (4,4 '-bis (3-aminophenoxy) diphenyl sulfone)
BAPP:2,2 '-two (the 4-[4-amino-benzene oxygen] phenyl) propane (2,2 '-bis (4-[4-aminophenoxy] phenyl) propane)
NMP:N-N-methyl-2-2-pyrrolidone N-(N-methyl-2-pyrrolidone)
TPP: triphenylphosphine (triphenylphosphine)
KBM403 (SHIN-ETSU HANTOTAI's chemical industry): γ-glycidoxy propyl group-Trimethoxy silane (γ-glycidoxypropyl-trimethoxysilane)
KBE402 (SHIN-ETSU HANTOTAI's chemical industry): γ-glycidoxy propyl group-methyl-diethoxy silane (γ-glycidoxypropyl-methyl-diethoxysilane)
Synthesis example one
Under logical nitrogen, the MBAA of 11.44 grams (40 mmole) is dissolved in the NMP three neck reaction flasks of 182.5 grams, ODPA with 31.02 grams (100 mmole) adds again, after treating its dissolving, stir the BAPP that adds 24.63 grams (60 mmole) after 1 hour again and restir 4 hours under room temperature, heat up after adding the toluene of 45 grams again, having water and methylbenzene azeotropic in the time of 155 ℃ produces, treat to be after its toluene is run out of fully that 180 ℃ are stirred after 2 hours down, cooling can obtain thickness polyimide solution PI-1.Get PI-1 solution 100 grams, add 3.6 gram KBM403, the 10%TPP (NMP) of 0.12 gram stirs under 120 ℃ and carried out modified-reaction in 3 hours, can get thickness thermoplastic polyimide resin solution TPI-1.
Synthesis example two
Under logical nitrogen, the DABZ of 6.08 grams (40 mmole) is dissolved in the NMP three neck reaction flasks of 156 grams, after again its dissolving being treated in the ODPA adding of 31.02 grams (100 mmole), stir the m-BAPS that adds 25.95 grams (60 mmole) after 1 hour again and restir 4 hours under room temperature, behind the toluene that adds 39 grams, heat up, having water and methylbenzene azeotropic in the time of 155 ℃ produces, treat to be after its toluene is run out of fully that 180 ℃ are stirred after 2 hours down, cooling can obtain thickness polyimide solution PI-2.Get PI-2 solution 100 grams, add 1.8 gram KBM403, the 10%TPP (NMP) of 0.12 gram stirs under 120 ℃ and carried out modified-reaction in 3 hours, can get thickness thermoplastic polyimide resin solution TPI-2.
Synthesis example three
Under logical nitrogen, the MBAA of 11.44 grams (40 mmole) is dissolved in the NMP three neck reaction flasks of 159 grams, after again its dissolving being treated in the BPADA adding of 52.05 grams (100 mmole), stir the BAPP that adds 24.63 grams (60 mmole) after 1 hour again and restir 4 hours under room temperature, behind the toluene that adds 40 grams, heat up, having water and methylbenzene azeotropic in the time of 155 ℃ produces, treat to be after its toluene is run out of fully that 180 ℃ are stirred after 2 hours down, cooling can obtain thickness polyimide solution PI-3.Get PI-3 solution 100 grams, add 3.6 gram KBM403, the 10%TPP (NMP) of 0.12 gram stirs under 120 ℃ and carried out modified-reaction in 3 hours, can get thickness thermoplastic polyimide resin solution TPI-3.
Synthetic comparative example one～three
Get PI-1 solution 100 grams, add 3.6 gram K3M403, the 10%TPP (NMP) of 0.12 gram, stirring under room temperature to get thickness TPI-1B solution.The 10%TPP (NMP) that in like manner PI-2 is added 1.8 gram KBM403 and 0.12 gram can get thickness TPI-2B, and the 10%TPP (NMP) that PI-3 adds 3.6 gram KBM403 and 0.12 gram can get thickness TPI-3B solution.
Synthetic comparative example four
Under logical nitrogen, the MBAA of 28.6 grams (40 mmole) is dissolved in the NMP three neck reaction flasks of 182.5 grams, after again its dissolving being treated in the ODPA adding of 31.02 grams (100 mmole), stir the BAPP that adds 24.63 grams (60 mmole) after 1 hour again and under room temperature restir 8 hours, can obtain polyamic acid solution PAA-1.
Embodiment one～three
(TPI-1～TPI-3) evenly coats the PI basal plate upper and lower surface of 1mil with synthesis example one～three thermoplastic polyimide resin to utilize scraper, and via hot-air oven under 120 ℃, after 5 minutes soft the baking, again through 180 ℃ 10 minutes, 250 ℃ 10 minutes, just can obtain up and down that thickness is the thermoplastic polyimide film of 5 μ m respectively, get final product among the double-sided metal foil layer laminated board between the polyimide resin layer material.(Furukawa Copper Foil, 1/2Qz F2-WS) utilize the hot pressing mode to form double-sided metal foil layer laminated board with thermoplastic polyimide resin, and wherein the pressure of hot pressing is 80Kg/cm with Copper Foil more at last
2, 350 ℃ of temperature, 20 minutes time.Copper foil laminates then and anti-scolding tin (288 ℃, 30sec) characteristic such as table one.Stripping strength is measured according to IPC-TM-650 (2.4.9), and soldering resistance is to assess according to IPC-TM-650 (2.4.13).
Comparative example one～four
With embodiment one～three, but (TPI-1～TPI-3) changes TPI-1B, TPI-2B, TPI-3B, the PAA-1 solution of synthetic comparative example one～four into synthesis example one～three thermoplastic polyimide resin.Copper foil laminates then and anti-scolding tin (288 ℃, 30sec) characteristic such as table one.
Comparative example five
Get the then soft two-sided copper foil base plate materials of formulation of the existing nothing of emerging product company of space portion, model BE1210 (polyimide=25um, ED Cu=18um), its centre material resin layer (UPILEX-VT) structure is respectively thermoplastic polyimide resin/polyimide resin/thermoplastic polyimide resin three-decker, measures its material behavior and incorporates table one and one comparison of various embodiments of the present invention do into.
Table one
| Double-sided metal foil layer laminated board | Embodiment | Embodiment | Embodiment | Comparative example | Comparative example | Comparative example | Comparative example four | Comparative example five |
| The epoxy silane addition manner | Reaction | Reaction | Reaction | Blending | Blending | Blending | Do not add | |
| Stitching surface stripping strength (lb/in) | 6.6 | 6.2 | 7.6 | 3.8 | 3.1 | 3.1 | 6.6 | 6.2 |
| Anti-scolding tin characteristic (288 ℃ of * 30sec) | By | By | By | By | By | By | Not good | By |
Can be found out that by table one embodiment one～three utilizes epoxy silane to carry out modified-reaction, the stripping strength of obtained copper foil laminates is all greater than 6lb/in, and the anti-scolding tin that passed through 288 ℃, 30 seconds is tested.In comparison, comparative example one～three just carries out blending with epoxy silane, though copper foil laminates can be by anti-scolding tin test, then property is not good; And comparative example four does not add epoxy silane, although then property is good, and can't be by anti-scolding tin test.
Claims (25)
1. thermoplastic polyimide combination comprises:
(A) silane-modified polyimide; And
(B) polar solvent, wherein
(A) silane-modified polyimide is (a) polyimide and the silane reaction gained that (b) has epoxide group, (a) polyimide is made of the repeating unit of following formula I and formula II, and the mole fraction at least 10% of formula II repeating unit, wherein X is the tetravalence aromatic base; Ar
1Be the divalence aromatic base; Ar
2For containing the divalence aromatic base of carboxylic acid group (COOH) or hydroxyl (OH),
Formula I formula II.
2. thermoplastic polyimide combination as claimed in claim 1, wherein X is selected from following tetravalence aromatic base:
3. thermoplastic polyimide combination as claimed in claim 1, wherein Ar
1Be selected from following divalence aromatic base:
4. thermoplastic polyimide combination as claimed in claim 1, wherein Ar
2Be selected from the divalence aromatic base of following carboxylic acid group of containing (COOH) or hydroxyl (OH):
5. thermoplastic polyimide combination as claimed in claim 1, its Chinese style II repeating unit is 30～60% at the mole fraction of (a) polyimide.
6. thermoplastic polyimide combination as claimed in claim 1, wherein (b) has the oxirane TMOS that the silane of epoxide group is non-aromatic.
7. thermoplastic polyimide combination as claimed in claim 6, wherein (b) to have the silane of epoxide group be oxirane ring ethyl organoalkoxysilane or glycidoxy propyl group organoalkoxysilane.
8. thermoplastic polyimide combination as claimed in claim 1 wherein also comprises: inorganic additives.
9. thermoplastic polyimide combination as claimed in claim 8, wherein this inorganic additives is selected from following at least a: silicon-dioxide, lime carbonate, talcum powder or clay.
10. thermoplastic polyimide combination as claimed in claim 1 wherein is somebody's turn to do the solid content 15-30 weight % of (A) silane-modified polyimide.
11. thermoplastic polyimide combination as claimed in claim 1, wherein this polar solvent is selected from: N-N-methyl-2-2-pyrrolidone N-, N,N-dimethylacetamide, gamma-butyrolactone, dimethylbenzene, toluene or aforesaid combination.
12. as the thermoplastic polyimide combination of claim 11, wherein this polar solvent is the N-N-methyl-2-2-pyrrolidone N-.
13. the making method of a double-surface flexible copper foil substrate comprises:
The solution that contains polyimide is provided, and this polyimide is made of following formula I and formula II repeating unit, and the mole fraction at least 10% of formula II repeating unit, and wherein X is tetravalence aromatic base, Ar
1Be divalence aromatic base, Ar
2For containing the divalence aromatic base of carboxylic acid group (COOH) or hydroxyl (OH);
Silane and the reaction of this polyimide to have epoxide group in above-mentioned solution form silane-modified thermoplastic polyimide;
Thermoplastic polyimide after the above-mentioned modification is coated the both sides of polyimide basal plate; And
To be coated with basal plate and two Copper Foil hot pressings of thermoplastic polyimide, form double-surface flexible copper foil substrate.
14. as the making method of the double-surface flexible copper foil substrate of claim 13, wherein this hot pressing step is less than 30 minutes, and do not carry out extra thermal treatment after the pressing.
15. as the making method of the double-surface flexible copper foil substrate of claim 13, the anti-scolding tin test of its prepared double-surface flexible copper foil substrate by 288 ℃, 30 seconds, and stripping strength is greater than 6lb/in.
16. as the making method of the double-surface flexible copper foil substrate of claim 13, wherein X is selected from following tetravalence aromatic base:
17. as the making method of the double-surface flexible copper foil substrate of claim 13, wherein Ar
1Be selected from following divalence aromatic base:
18. as the making method of the double-surface flexible copper foil substrate of claim 13, wherein Ar2 is selected from the divalence aromatic base of following carboxylic acid group of containing (COOH) or hydroxyl (OH):
19. as the making method of the double-surface flexible copper foil substrate of claim 13, its Chinese style II repeating unit is 30～60% at the mole fraction of (a) polyimide.
20. as the making method of the double-surface flexible copper foil substrate of claim 13, wherein (b) has the oxirane TMOS that the silane of epoxide group is non-aromatic.
21. as the making method of the double-surface flexible copper foil substrate of claim 20, wherein (b) to have the silane of epoxide group be epoxycyclohexyl organoalkoxysilane or glycidoxy propyl group organoalkoxysilane.
22. the making method as the double-surface flexible copper foil substrate of claim 13 wherein also comprises: add inorganic additives in this silane-modified thermoplastic polyimide.
23. as the making method of the double-surface flexible copper foil substrate of claim 22, wherein this inorganic additives is selected from following at least a: silicon-dioxide, lime carbonate, talcum powder or clay.
24. as the making method of the double-surface flexible copper foil substrate of claim 13, wherein the content of polyimide is 15-30 weight % in this solution.
25. as the making method of the double-surface flexible copper foil substrate of claim 13, wherein this has the silane of epoxide group and the molar ratio of this polyimide is 1:1～1:3.
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| CN101787126B (en) * | 2009-12-24 | 2013-06-12 | 广东生益科技股份有限公司 | Polyamide acid composition, method for manufacturing two-layer process flexible copper-clad plates by use of same, and obtained two-layer process flexible copper-clad plate |
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| CN102281717B (en) * | 2011-08-06 | 2013-04-03 | 倪新军 | Manufacture method for base plate of high frequency circuit module |
| KR101416782B1 (en) * | 2012-04-24 | 2014-07-08 | 에스케이이노베이션 주식회사 | Flexilbe Metal Clad Laminate |
| CN102922819A (en) * | 2012-11-16 | 2013-02-13 | 江苏科技大学 | Preparation method of non-adhesive double-sided copper-clad foil with high smoothness |
| CN103192563A (en) * | 2013-04-24 | 2013-07-10 | 昆山翰辉电子科技有限公司 | Composite double-faced copper foil substrate for flexible printed circuit board |
| KR101583876B1 (en) | 2013-11-11 | 2016-01-12 | 주식회사 이그잭스 | Composition of photo sensitive resin including polyimide precursor |
| KR102103157B1 (en) * | 2015-04-17 | 2020-04-22 | 아사히 가세이 가부시키가이샤 | Resin composition, polyimide resin film, and method for producing same |
| CN109337066B (en) * | 2018-09-28 | 2020-08-11 | 浙江大学 | Reactive and easily-soluble rigid chain polymer and preparation method and composition thereof |
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