CN101121819A - Modified maleimide end-sealed type polyimide resin composite and application thereof - Google Patents
Modified maleimide end-sealed type polyimide resin composite and application thereof Download PDFInfo
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- CN101121819A CN101121819A CNA200710053374XA CN200710053374A CN101121819A CN 101121819 A CN101121819 A CN 101121819A CN A200710053374X A CNA200710053374X A CN A200710053374XA CN 200710053374 A CN200710053374 A CN 200710053374A CN 101121819 A CN101121819 A CN 101121819A
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- Prior art keywords
- polyimide resin
- sealed type
- type polyimide
- maleimide end
- solution
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- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 63
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title description 2
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 title 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 41
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 29
- 239000011889 copper foil Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000011049 filling Methods 0.000 claims abstract description 12
- -1 allyl compound Chemical class 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 27
- 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 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 150000005690 diesters Chemical class 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 150000004985 diamines Chemical class 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 125000000746 allylic group Chemical group 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- 238000009775 high-speed stirring Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 6
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 4
- SHALVKVVWYJLCA-UHFFFAOYSA-N propane-1,1,1,2-tetracarboxylic acid Chemical compound OC(=O)C(C)C(C(O)=O)(C(O)=O)C(O)=O SHALVKVVWYJLCA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 3
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical class C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 3
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 2
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 14
- 229920005989 resin Polymers 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000002788 crimping Methods 0.000 abstract 1
- 238000005476 soldering Methods 0.000 abstract 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 10
- 239000004642 Polyimide Substances 0.000 description 9
- 229960004756 ethanol Drugs 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 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 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention is a modified maleimide-terminated polyimide resin compound and the application. The compound mainly consists of the maleimide-terminated polyimide resin, the allyl compound and the inorganic filling material. The maleimide-terminated polyimide resin uses the N-methyl-2-pyrrolidone as the solvent and is synthesized by the temperature-changing imidization method. The addition of the inorganic filling material of a certain amount in the modified resin obviously improves the permissible range of the thermal expansion coefficient differences between the polyimide film layer and the copper foil. The non-gel two-story flexible covering copper plate made by the modified terminated polyimide resin has the excellent heat resistance and can apply to the lead-free soldering; non-gel two-story flexible covering copper plate has the small crimping performance is small, the non-porous surface, the good dimensional stability, the good mechanical strength, the high peeling strength and folding endurance, and at the same time, has the low thermal expansion coefficient, dielectric constant and water-absorption rate.
Description
Technical field:
The present invention relates to flexible printed circuit with flexible copper-clad plate substrate and field of compound material thereof, is about the synthetic method of maleimide end-sealed type polyimide resin and preparation and its application on a kind of gum-free two-layer method flexibility coat copper plate of modified resin composition thereof.
Technical background:
The Chinese invention patent application number of submitting to as the inventor is described in 200710053151.3 the specification sheets, at present, fast development along with electronic industry, the outward appearance and the performance requriements of electronic product are more and more higher, the electronic product of short, little, light, thin, U.S. and excellent comprehensive performance has become manufacturer and human consumer's first-selection, thus the base material of flexible printed-circuit board inevitably by the three-layer process product that the glue type is arranged towards two layers of method production development of more frivolous gum-free.
The gum-free two-layer method flexibility coat copper plate is that matrix resin directly is adhered to copper foil surface, produce the matrix resin layers of combining closely with Copper Foil, because of not having traditional epoxies or acrylic resin as bond layer, it has glue type three-layer process product with respect to tradition, and over-all properties is better.According to the literature, two layers of method product of this type of gum-free are mainly obtained by three kinds of methods: it forms copper conductive layer on the Kapton surface by electroless plating and electric plating method just like reporting among the CN1114821; It two is reported as CN13273617, adopts vacuum sputtering technology or evaporation precipitation technology, copper is deposited on the insulating film, thereby forms flexibility coat copper plate; It three is that matrix resin or its precursor solution directly are coated on copper foil surface, under certain temperature, carries out aftertreatment through certain technology again, forms the polyimide rete that is adhered to copper foil surface.In above-mentioned the third method, report that maximum is directly to be coated on copper foil surface as the polyamic acid solution of polyimide precursor, carry out gradient increased temperature then, finally make it under the high temperature more than 350 ℃, finish imidization, formation is overlying on the polyimide of Copper Foil, thereby obtain the gum-free two-layer method flexibility coat copper plate (such as among CN1575092A and the CN1410471A report), the great advantage of this kind method is that production cost is low, technology is fairly simple.But because of use polyimide precursor solution---polyamic acid is very easily degraded, storage period is too short, can not satisfy the needs that large scale industry is produced well, and the control of the condition in its hot imidization process is very harsh, too high to the requirement of equipment and envrionment conditions.At this problem, the inventor is in Chinese patent application number is 200710053151.3 specification sheets, synthesized a kind of maleimide end-sealed type polyimide resin that dissolves in the imidization fully of polar solvent (as the N-N-methyl-2-2-pyrrolidone N-), with it with after allylic cpd mixes mutually, be made into the matrix resin homogeneous phase solution, directly be coated on copper foil surface, remove solvent after, at (in 260 ℃) crosslinking curing under the relatively low temperature, form the polyimide rete that is overlying on Copper Foil.The major advantage of this kind method is: matrix used resin is easily stored, easy to process, can ready access upon use, solidification value polyimide commonly used relatively precursor solution---polyamic acid is much lower, thereby in process of production the requirement of equipment and envrionment conditions is reduced greatly; Resin does not have the small molecules volatile matter when crosslinking curing emits, thereby can obtain the almost gum-free two-layer method flexibility coat copper plate base material of imperforate excellent combination property.
For the printed electronic circuit of miniaturization day by day, the dimensional stability of flexibility coat copper plate is a very important parameter, the flexibility coat copper plate that dimensional stability is good can not take place obviously to curl in the course of processing, therefore, the matrix resin that is used as the gum-free two-layer method flexibility coat copper plate is except its cementability, high-temperature stability and mechanical property all must meet the requirements, thermal expansion coefficient difference value between itself and the Copper Foil also must be controlled within the specific limits, and the flexibility coat copper plate that makes so just has dimensional stability preferably.The approach that solves the dimensional stability problem of gum-free two-layer method flexibility coat copper plate has two: one, can pass through screening formulation, and select for use material that the thermal expansivity of thermal expansivity and Copper Foil is close as matrix resin; Its two, by adding an amount of inorganic filling material, improve the tolerable limit of thermal expansion coefficient difference value between matrix resin and the Copper Foil, to reach the purpose of improvement flexibility coat copper plate dimensional stability.
About the problems referred to above, the present invention is on 200710053151.3 the basis at the Chinese invention patent application number, in the modified maleimide end-sealed type polyimide resin Composition, add different inorganic filling materials such as mica, talcum powder, barium sulfate, secondary calcium phosphate, silicon-dioxide or its mixture, through each copper-clad plate dimensional stability parameter is detected, find to add a certain amount of inorganic filling material, can obviously improve the tolerable limit of thermal expansion coefficient difference value between polyimide rete and the Copper Foil.Shown in embodiment in this specification sheets table one 2,3, its Coefficient of Thermal Expansion value reaches 27ppm/ ℃, 30ppm/ ℃ respectively, and it is a lot of that this value exceeds 17ppm/ ℃ of Copper Foil, but its dimensional stability still better (is used IPC-TM-650, the NO.2.2.4 standard detection, MD, TD value are all less than 0.05%).
Summary of the invention:
The object of the present invention is to provide a kind of modified maleimide end-sealed type polyimide resin combination and preparation method that the gum-free two-layer method flexibility coat copper plate is produced that be used for.This resin combination has excellent thermotolerance, dimensional stability, anti-bending, workability and low-k, the low-dielectric loss factor.
Another purpose of invention is to provide a kind of new synthetic method of the maleimide end-sealed type polyimide resin as one of described composition component.
Another object of the present invention is to provide the application method of a kind of modified maleimide end-sealed type polyimide resin combination on the gum-free two-layer method flexibility coat copper plate.
The technical scheme that reaches above-mentioned purpose of the present invention is:
A kind of composition of modified maleimide end-sealed type polyimide resin combination and weight proportion are:
100 parts of maleimide end-sealed type polyimide resins
4～50 parts of allylic cpds
10～35 parts of inorganic filling materials
Wherein, described allylic cpd is a kind of or the two blend in diallyl bisphenol and the diallyl bisphenol S;
Described inorganic filling material is one or more blends in mica, talcum powder, barium sulfate, secondary calcium phosphate, the silicon-dioxide, and particle diameter is less than 1 micron.It must have certain addition to be enough to have an effect, and is example with mica and talcum powder, and addition reaches more than 10% of maleimide end-sealed type polyimide resin demand, and preferable effect is just arranged.
In the prescription of modified resin system, the consumption of allylic cpd is chosen to be 4%～50% of maleimide end-sealed type polyimide resin demand, if the consumption of allylic cpd is less than 4%, then the toughness of system is relatively poor, if its consumption is greater than 50%, then the thermotolerance of system and dielectric properties reduce significantly.
The preparation method of above-mentioned maleimide end-sealed type polyimide resin, it is characterized in that, with aromatic tetrahydric dianhydride, diamine and MALEIC ANHYDRIDE is raw material, and the ratio of the amount of substance of aromatic tetrahydric dianhydride, diamine and MALEIC ANHYDRIDE is n: (n+1): 2, and building-up process is:
A) aromatic tetrahydric dianhydride is made into reaction solution with the low-boiling point alcohol kind solvent, 1 gram aromatic tetrahydric dianhydride is with 7～10 milliliters of solvents, under nitrogen protection, refluxed 1～5 hour, obtain corresponding two acid diesters, alcoholic solvent is steamed, residual alcoholic solvent under reduced pressure eliminates;
B) with the mixed solvent dissolving of diamine with chlorobenzene and N-N-methyl-2-2-pyrrolidone N-, chlorobenzene and N-N-methyl-2-2-pyrrolidone N-volume ratio are 1: 4～8, gained solution is joined in two acid diesters that step a) obtains, after fully stirring, under 160 ℃～180 ℃ temperature, back flow reaction 6～30 hours generates amino-terminated polyimide resin solution, naturally cooling;
C) in the solution that step b) obtains, add MALEIC ANHYDRIDE, after reacting 3～24 hours under the room temperature, add chlorobenzene, make the volume ratio of chlorobenzene and N-N-methyl-2-2-pyrrolidone N-become 2～3: 1, under 130 ℃～132 ℃, reflux water-dividing 24～36 hours, after the cooling reaction solution is poured in the dehydrated alcohol of high-speed stirring, obtain throw out, after the gained throw out was successively used dehydrated alcohol and anhydrous diethyl ether thorough washing, vacuum-drying promptly got the maleimide end-sealed type polyimide resin.
Reaction process as the formula (1),
In the formula; N is the resin polymerization degree, 1≤n≤20; Aromatic tetrahydric dianhydride is O (CO)
2R
1(CO)
2Diamine is H
2N-R
2-NH
2
Above-mentioned steps is selected aromatic tetrahydric dianhydride monomer O (CO) a)
2R
1(CO)
2, what wherein be suitable for can enumerate R
1For as the formula (2).Wherein X is O, S, SO
2, CO, CH
2, C (CH
3)
3, CF
2, C (CF
3)
2Perhaps do not exist.R
1Substituting group can be arranged, but preferably do not have substituting group, or C
1～C
6Low alkyl group or lower alkoxy.When synthetic maleimide end-sealed type polyimide resin, can use single aromatic tetrahydric dianhydride, the mixture that also can select for use two kinds or more aromatic tetrahydric dianhydrides to form.Preferred aromatic tetrahydric dianhydride has: 3,3 ', 4,4 '-BPDA (BPDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 2,2 '-it is two that [4-(3,4-dicarboxyl phenoxy group) phenyl] propane tetracarboxylic dianhydride (BPADA), 2,2 '-two (3,4-two carboxyphenyls) HFC-236fa tetracarboxylic dianhydride (6FDA).Five amount can not be zero simultaneously, and wherein any one amount of substance mark that accounts for the aromatic tetrahydric dianhydride blend is 0%～100%;
Above-mentioned steps b) selected diamine H
2N-R
2-NH
2, the enumerated R of Shi Yonging wherein
2As the formula (3).Wherein Z is O, S, SO
2, CO, CH
2, C (CH
3)
3, CF
2, C (CF
3)
2Perhaps do not exist; R
2Be C
1～C
6Low alkyl group or lower alkoxy; R
3Be C
1～C
12Alkyl or-oxyl; R
4Be methyl, ethyl or the tertiary butyl; When synthetic maleimide end-sealed type polyimide resin, can select wherein a kind of, two kinds or multiple diamine monomer mixture for use.Preferred diamine has: 1, two (the 3-aminopropane base) tetramethyl disiloxanes of 3-, 1, two (the 4-amino-benzene oxygen methane)-1,1,3 of 3-, the 3-tetramethyl disiloxane, 4,4 '-diaminodiphenylsulfone(DDS), 2, two [(4-amino-benzene oxygen) phenyl] propane of 2-, 3,3 ', 5,5 '-tetramethyl--4,4 '-diaminodiphenylmethane, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 1, two (4-the amino-benzene oxygen)-2-tert.-butylbenzenes of 4-, 1, two (the 4-amino-benzene oxygens)-2 of 4-, 5-di-tert-butyl, eight amount can not be zero simultaneously, and wherein any one amount of substance mark that accounts for the diamine blend is 0%～100%.
React described low-boiling point alcohol kind solvent and be a kind of or the two blend in anhydrous methanol, the dehydrated alcohol.
The application of modified maleimide end-sealed type polyimide resin combination of the present invention on the gum-free two-layer method flexibility coat copper plate, its special character is:
According to above-mentioned maleimide end-sealed type polyimide resin; allylic cpd and inorganic filling material ratio of weight and number take by weighing raw material; after its mixing; promptly get the modified maleimide end-sealed type polyimide resin combination; it is dissolved in the polar solvent; fully stir; the formation solid content is 10%～50% homogeneous phase solution; this solution is coated on the Copper Foil of 5 microns～35 micron thickness; control liquid film thickness after solvent evaporates is 10 microns～30 microns; in high temperature oven; under nitrogen protection, carry out gradient increased temperature and solidify, promptly get the gum-free two-layer method flexibility coat copper plate.
The polar solvent of above-mentioned soluble modified maleimide end-sealed type polyimide resin composite is N-N-methyl-2-2-pyrrolidone N-(NMP), N, N '-dimethyl formamide (DMF), N, N '-N,N-DIMETHYLACETAMIDE (DMAc), dimethyl sulfoxide (DMSO) (DMSO), meta-cresol, methyl-sulfate, tetramethylene sulfone, butyrolactone, tetrahydrofuran (THF) etc.Wherein preferred N-N-methyl-2-2-pyrrolidone N-(NMP), N, N '-dimethyl formamide (DMF), N, a kind of or several mixtures in N '-N,N-DIMETHYLACETAMIDE (DMAc), the dimethyl sulfoxide (DMSO) (DMSO).
Above-mentioned gradient increased temperature curing process is: 80 ℃ * 1 hour, and 120 ℃ * 1 hour, 180 ℃ * 1 hour, 260 ℃ * 1 hour.
The adhesive surface of above-mentioned used Copper Foil (applying the one side of homogeneous phase solution) has carried out chemistry or physics roughened.
Major advantage of the present invention is:
With the N-N-methyl-2-2-pyrrolidone N-is solvent, adopts the maleimide end-sealed type polyimide resin of the synthetic complete imidization of alternating temperature solution imidization method, and its pressed powder is easily stored, and may be dissolved in the polar solvent of selecting for use, and is easy to process, can ready access upon use.With the homogeneous phase solution of modified resin composition preparation good stability at room temperature, wherein, an amount of inorganic filling material that adds in modified resin composition has obviously improved the tolerable limit of thermal expansion coefficient difference value between polyimide rete and the Copper Foil.Be used on the gum-free two-layer method flexibility coat copper plate, production cost is low, technology is simple.Its solidification value polyimide commonly used relatively precursor solution---polyamic acid is much lower, thereby in process of production the requirement of equipment and envrionment conditions is reduced greatly.Resin does not have the small molecules volatile matter when solidifying emits, thereby can obtain the almost gum-free two-layer method flexibility coat copper plate base material of imperforate excellent combination property.
Embodiment:
The present invention further specifies with following example, but the present invention is not limited to these examples.
Embodiment 1
Under nitrogen protection; with 3; 3 '; 4; 4 '-benzophenone tetracarboxylic dianhydride 32.265 gram (0.10 mole) refluxes in 250 ml methanol and obtained corresponding two acid diesters in 1～5 hour; methyl alcohol is steamed, and residual methyl alcohol under reduced pressure eliminates, with 27.338 gram (0.11 moles) 1; two (the 3-aminopropane base) tetramethyl disiloxanes of 3-; with joining in two acid diesters after 31 milliliters of chlorobenzenes and the dissolving of 123 milliliters of N-N-methyl-2-2-pyrrolidone N-s, after fully stirring, under 164 ℃; reacted 6 hours; generate amino-terminated polyimide resin solution, treat its cold naturally after, add MALEIC ANHYDRIDE 1.961 grams (0.02 mole); reaction is after 8 hours under the room temperature; add 205 milliliters of chlorobenzenes, under 132 ℃, reflux water-dividing 32 hours; after the cooling reaction solution is poured in the dehydrated alcohol of high-speed stirring; obtain throw out, after the gained throw out was successively used dehydrated alcohol and anhydrous diethyl ether thorough washing, vacuum-drying promptly got maleimide end-sealed type polyimide resin 51.80 grams.
Take by weighing above-mentioned maleimide end-sealed type polyimide resin 50 grams, diallyl bisphenol 2.5 grams and mica 5 grams, after the three is mixed, be dissolved among 190 milliliters of NMP, fully stir into homogeneous phase solution.With this solution be coated to 35 micron thickness on the Copper Foil that the physics roughened is crossed; control liquid film thickness after solvent evaporates is 10 microns～30 microns; in high temperature oven; under nitrogen protection, carry out gradient increased temperature; temperature-rise period is: 80 ℃ * 1 hour; 120 ℃ * 1 hour, 180 ℃ * 1 hour, 260 ℃ * 1 hour.Slowly cool to room temperature and promptly get the gum-free two-layer method flexibility coat copper plate.
Embodiment 2
Under nitrogen protection; with 3; 3 '; 4,4 '-phenyl ether tetracarboxylic dianhydride 24.851 gram (0.08 mole) refluxes in 174 milliliters of ethanol and obtained corresponding two acid diesters in 1～5 hour, ethanol is steamed; residual ethanol under reduced pressure eliminates; with 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane 20.369 grams (0.09 mole); after 20 milliliters of chlorobenzenes and the dissolving of 98 milliliters of N-N-methyl-2-2-pyrrolidone N-s; join in two acid diesters, after fully stirring, under 168 ℃; reacted 10 hours; generate amino-terminated polyimide resin solution, treat its cold naturally after, add MALEIC ANHYDRIDE 1.961 grams (0.02 mole); reaction is after 12 hours under the room temperature; add 274 milliliters of chlorobenzenes, under 130 ℃, reflux water-dividing 36 hours; after the cooling reaction solution is poured in the dehydrated alcohol of high-speed stirring; obtain throw out, after the gained throw out was successively used dehydrated alcohol and anhydrous diethyl ether thorough washing, vacuum-drying promptly got maleimide end-sealed type polyimide resin 41.50 grams.
Take by weighing above-mentioned maleimide end-sealed type polyimide resin 30 grams, diallyl bisphenol 5.0 grams and talcum powder 6 grams, after the three is mixed, be dissolved among 140 milliliters of DMAc, fully stir into homogeneous phase solution.This solution is coated on the Copper Foil of 35 micron thickness, control liquid film thickness after solvent evaporates is 10 microns～30 microns, in high temperature oven; carry out gradient increased temperature under nitrogen protection, temperature-rise period is: 80 ℃ * 1 hour, and 120 ℃ * 1 hour; 180 ℃ * 1 hour, 260 ℃ * 1 hour.Slowly cool to room temperature and promptly get the gum-free two-layer method flexibility coat copper plate.
Embodiment 3
Under nitrogen protection; with 3; 3 '; 4; 4 '-BPDA 8.827 grams (0.03 mole) and 3; 3 '; 4; 4 '-benzophenone tetracarboxylic dianhydride 19.359 gram (0.06 mole) refluxes in 230 ml methanol and obtained corresponding two acid diesters in 1～5 hour; methyl alcohol is steamed; residual methyl alcohol under reduced pressure eliminates; with two (4-amino-benzene oxygen)-2-tert.-butylbenzene 13.938 grams (0.04 mole) of 1.4-; 1.4-two (4-amino-benzene oxygen)-2.5-di-tert-butyl 24.273 grams (0.06 mole); after 25 milliliters of chlorobenzenes and the dissolving of 150 milliliters of N-N-methyl-2-2-pyrrolidone N-s; join in two acid diesters; after fully stirring; under 172 ℃, reacted 16 hours, generate amino-terminated polyimide resin solution; treat its cold naturally after; add MALEIC ANHYDRIDE 1.961 grams (0.02 mole), reaction added 425 milliliters of chlorobenzenes after 24 hours under the room temperature; under 130 ℃; reflux water-dividing 29 hours is poured reaction solution in the dehydrated alcohol of high-speed stirring after the cooling, obtains throw out; after the gained throw out was successively used dehydrated alcohol and anhydrous diethyl ether thorough washing, vacuum-drying promptly got maleimide end-sealed type polyimide resin 61.05 grams.
Take by weighing above-mentioned maleimide end-sealed type polyimide resin 50 grams, diallyl bisphenol 7.5 grams and barium sulfate 10 grams, after the three is mixed, be dissolved among 230 milliliters of DMF, fully stir into homogeneous phase solution.With this solution be coated to 35 micron thickness on the Copper Foil that the physics roughened is crossed; control liquid film thickness after solvent evaporates is 10 microns～30 microns; in high temperature oven; under nitrogen protection, carry out gradient increased temperature; temperature-rise period is: 80 ℃ * 1 hour; 120 ℃ * 1 hour, 180 ℃ * 1 hour, 260 ℃ * 1 hour.Slowly cool to room temperature and promptly get the gum-free two-layer method flexibility coat copper plate.
Embodiment 4
Under nitrogen protection; with 2; 2 '-it is two that [4-(3; 4-dicarboxyl phenoxy group) phenyl] propane tetracarboxylic dianhydride 52.049 grams (0.10 mole) and 2; 2 '-two (3; 4-two carboxyphenyls) HFC-236fa tetracarboxylic dianhydride 22.212 grams (0.05 mole) reflux in 590 milliliters of ethanol and obtained corresponding two acid diesters in 1～5 hour; ethanol is steamed; residual ethanol under reduced pressure eliminates; with 4; 4 '-diaminodiphenylsulfone(DDS), 4.966 grams (0.02 mole); 1.4-two (4-amino-benzene oxygen)-2-tert.-butylbenzene 34.845 grams (0.10 mole); and 1; two (the 4-amino-benzene oxygen methane)-1 of 3-; 1; 3; 3-tetramethyl disiloxane 15.064 (0.04 mole); after 47 milliliters of chlorobenzenes and the dissolving of 285 milliliters of N-N-methyl-2-2-pyrrolidone N-s; join in two acid diesters; after fully stirring; under 1 72 ℃; reacted 12 hours; generate amino-terminated polyimide resin solution, treat its cold naturally after, add MALEIC ANHYDRIDE 1.961 grams (0.02 mole); reaction is after 14 hours under the room temperature; add 665 milliliters of chlorobenzenes, under 131 ℃, reflux water-dividing 28 hours; after the cooling reaction solution is poured in the dehydrated alcohol of high-speed stirring; obtain throw out, after the gained throw out was successively used dehydrated alcohol and anhydrous diethyl ether thorough washing, vacuum-drying promptly got maleimide end-sealed type polyimide resin 100.14 grams.
Take by weighing above-mentioned maleimide end-sealed type polyimide resin 60 grams, diallyl bisphenol 18 grams and secondary calcium phosphate 15 grams, after the three is mixed, be dissolved among 300 milliliters of DMSO, fully stir into homogeneous phase solution.This solution is coated on the Copper Foil of 35 micron thickness, control liquid film thickness after solvent evaporates is 10 microns～30 microns, in high temperature oven; carry out gradient increased temperature under nitrogen protection, temperature-rise period is: 80 ℃ * 1 hour, and 120 ℃ * 1 hour; 180 ℃ * 1 hour, 260 ℃ * 1 hour.Slowly cool to room temperature and promptly get the gum-free two-layer method flexibility coat copper plate.
Embodiment 5
Under nitrogen protection; with 3; 3 '; 4; 4 '-benzophenone tetracarboxylic dianhydride, 9.680 grams (0.03 mole); 2; 2 '-it is two that [4-(3; 4-dicarboxyl phenoxy group) phenyl] propane tetracarboxylic dianhydride 15.615 (0.03 mole) and 3; 3 '; 4; 4 '-BPDA, 8.827 grams (0.03 mole) reflux in 240 milliliters of ethanol and obtained corresponding two acid diesters in 1～5 hour; ethanol is steamed; residual ethanol under reduced pressure eliminates; will be with 24 milliliters of chlorobenzenes and 134 milliliters of N-N-methyl-2-2-pyrrolidone N-institute dissolved 3; 3 '-dimethyl-4; 4 '-diaminodiphenylmethane, 11.316 grams (0.05 mole); 1.4-two (4-amino-benzene oxygen)-2-tert.-butylbenzene 6.969 grams (0.02 mole); and 1; two (the 4-amino-benzene oxygen methane)-1 of 3-; 1; 3; 3-tetramethyl disiloxane 9.415 (0.025 mole) joins in two acid diesters; after fully stirring; under 170 ℃, reacted 18 hours, generate amino-terminated polyimide resin solution; treat its cold naturally after; add MALEIC ANHYDRIDE 0.981 gram (0.01 mole), reaction added 350 milliliters of chlorobenzenes after 12 hours under the room temperature; under 130 ℃; reflux water-dividing 33 hours is poured reaction solution in the dehydrated alcohol of high-speed stirring after the cooling, obtains throw out; after the gained throw out was successively used dehydrated alcohol and anhydrous diethyl ether thorough washing, vacuum-drying promptly got maleimide end-sealed type polyimide resin 58.51 grams.
Take by weighing above-mentioned maleimide end-sealed type polyimide resin 50 grams, diallyl bisphenol 4 grams and silicon-dioxide 8 grams, after the three is mixed, be dissolved among 210 milliliters of DMAc, fully stir into homogeneous phase solution.This solution is coated on the Copper Foil of 35 micron thickness, control liquid film thickness after solvent evaporates is 10 microns～30 microns, in high temperature oven; carry out gradient increased temperature under nitrogen protection, temperature-rise period is: 80 ℃ * 1 hour, and 120 ℃ * 1 hour; 180 ℃ * 1 hour, 260 ℃ * 1 hour.Slowly cool to room temperature and promptly get the gum-free two-layer method flexibility coat copper plate.
The test performance of the gum-free two-layer method flexibility coat copper plate of above-mentioned examples preparation is as shown in table 1.
The test performance of table 1 gum-free two-layer method flexibility coat copper plate
| Test event | Test condition | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Testing method |
| Thermal expansivity | 100-200℃ | ppm | 15 | 27 | 30 | 16 | 20 | TMA |
| Second-order transition temperature | A | ℃ | 286 | 292 | 288 | 289 | 298 | DSC |
| Flame resistivity | A | - | V-0 | V-0 | V-0 | V-0 | V-0 | UL94 |
| Dimensional stability | MD | ％ | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | IPC-TM-650， NO.2.2.4 |
| TD | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | |||
| Anti-tin-welding | 300℃/60s | - | Qualified | Qualified | Qualified | Qualified | Qualified | IPC-TM-650， NO.2.4.13 |
| Anti-bending | MD | Inferior | ＞4000 | ＞4000 | ＞4000 | ＞4000 | ＞4000 | JIS6471， (0.8R、0.5kg) |
| TD | ＞4000 | ＞4000 | ＞4000 | ＞4000 | ＞4000 | |||
| Surface resistivity | A | Ω | ＞10 14 | ＞10 14 | ＞10 14 | ＞10 14 | ＞10 14 | IPC-TM-650， NO.2.5.17 |
| Volume resistance | A | Ωcm | ＞10 14 | ＞10 14 | ＞10 14 | ＞10 14 | ＞10 14 | IPC-TM-650， NO.2.5.17 |
| Water-intake rate | A | ％ | ＜1.0 | ＜1.0 | ＜1.0 | ＜1.0 | ＜1.0 | IPC-TM-650， NO.2.6.2 |
| Specific inductivity | A | - | ＜3.5 | ＜3.5 | ＜3.5 | ＜3.5 | ＜3.5 | IPC-TM-650， NO.2.5.5.3 |
| Tensile strength | A | Mpa | ＞400 | ＞400 | ＞400 | ＞400 | ＞400 | IPC～TM-650， NO.2.4.19 |
| Stripping strength | A | Kgf/cm | ＞1.0 | ＞1.0 | ＞1.0 | ＞1.0 | ＞1.0 | IPC-TM-650， NO.2.4.9 |
Claims (8)
1. modified maleimide end-sealed type polyimide resin combination, it is characterized in that: the composition of described composition and weight proportion are:
100 parts of maleimide end-sealed type polyimide resins
4～50 parts of allylic cpds
10～35 parts of inorganic filling materials;
Described allylic cpd is a kind of or the two blend in diallyl bisphenol and the diallyl bisphenol S;
Described inorganic filling material is one or more blends in mica, talcum powder, barium sulfate, secondary calcium phosphate, the silicon-dioxide, and its particle diameter is less than 1 micron.
2. the preparation method of a maleimide end-sealed type polyimide resin, it is characterized in that, with aromatic tetrahydric dianhydride, diamine and MALEIC ANHYDRIDE is raw material, and the ratio of the amount of substance of aromatic tetrahydric dianhydride, diamine and MALEIC ANHYDRIDE is n: (n+1): 2, and building-up process is:
A) aromatic tetrahydric dianhydride is used low-boiling point alcohol kind solvent wiring solution-forming, 1 gram aromatic tetrahydric dianhydride is with 7～10 milliliters of solvents, under nitrogen protection, refluxed 1～5 hour, obtain corresponding two acid diesters, alcoholic solvent is steamed, residual alcoholic solvent under reduced pressure eliminates;
B) with the mixed solvent dissolving of diamine with chlorobenzene and N-N-methyl-2-2-pyrrolidone N-, chlorobenzene and N-N-methyl-2-2-pyrrolidone N-volume ratio are 1: 4～8, gained solution is joined in two acid diesters that step a) obtains, after fully stirring, under 160 ℃～180 ℃ temperature, back flow reaction 6～30 hours generates amino-terminated polyimide resin solution, naturally cooling;
C) in the solution that step b) obtains, add MALEIC ANHYDRIDE, after reacting 3～24 hours under the room temperature, add chlorobenzene, make the volume ratio of chlorobenzene and N-N-methyl-2-2-pyrrolidone N-become 2～3: 1, under 130 ℃～132 ℃, reflux water-dividing 24～36 hours, after the cooling reaction solution is poured in the dehydrated alcohol of high-speed stirring, obtain throw out, after the gained throw out was successively used dehydrated alcohol and anhydrous diethyl ether thorough washing, vacuum-drying promptly got the maleimide end-sealed type polyimide resin;
Wherein, the described aromatic tetrahydric dianhydride of step a) be 3,3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 2,2 '-it is two that [4-(3,4-dicarboxyl phenoxy group) phenyl] propane tetracarboxylic dianhydride, 2,2 '-two (3,4-two carboxyphenyls) HFC-236fa tetracarboxylic dianhydride, five amount can not be zero simultaneously, and wherein any one amount of substance mark that accounts for the aromatic tetrahydric dianhydride blend is 0%～100%;
The described diamine of step b) is 1, two (the 3-aminopropane base) tetramethyl disiloxanes of 3-, 1, two (the 4-amino-benzene oxygen methane)-1,1,3 of 3-, the 3-tetramethyl disiloxane, 4,4 '-diaminodiphenylsulfone(DDS), 2, two [(4-amino-benzene oxygen) phenyl] propane of 2-, 3,3 ', 5,5 '-tetramethyl--4,4 '-diaminodiphenylmethane, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 1, two (4-the amino-benzene oxygen)-2-tert.-butylbenzenes of 4-, 1, two (the 4-amino-benzene oxygens)-2 of 4-, 5-di-tert-butyl, eight amount can not be zero simultaneously, and wherein any one amount of substance mark that accounts for the diamine blend is 0%～100%.
3. the preparation method of maleimide end-sealed type polyimide resin according to claim 2 is characterized in that: described low-boiling point alcohol kind solvent is a kind of or the two blend in anhydrous methanol, the dehydrated alcohol.
4. the application of the described modified maleimide end-sealed type polyimide resin combination of claim 1; it is characterized in that: be applied on the gum-free two-layer method flexibility coat copper plate; usage is according to described maleimide end-sealed type polyimide resin; allylic cpd and inorganic filling material ratio of weight and number take by weighing raw material; after three's mixing; be dissolved in the polar solvent; fully stir; the formation solid content is 10%～50% homogeneous phase solution; this solution is coated on the Copper Foil of 5 microns～35 micron thickness; control liquid film thickness after solvent evaporates is 10 microns～30 microns; in high temperature oven, under nitrogen protection, carry out gradient increased temperature curing and get final product.
5. the application of modified maleimide end-sealed type polyimide resin combination according to claim 4, it is characterized in that: described polar solvent is N-N-methyl-2-2-pyrrolidone N-, N, N '-dimethyl formamide, N, a kind of or several mixtures in N '-N,N-DIMETHYLACETAMIDE, the dimethyl sulfoxide (DMSO).
6. the application of modified maleimide end-sealed type polyimide resin combination according to claim 4 is characterized in that: the solid content of described homogeneous phase solution is 10%～50%.
7. the application of modified maleimide end-sealed type polyimide resin combination according to claim 4 is characterized in that: described gradient increased temperature curing process is: 80 ℃ * 1 hour, and 120 ℃ * 1 hour, 180 ℃ * 1 hour, 260 ℃ * 1 hour.
8. the application of modified maleimide end-sealed type polyimide resin combination according to claim 4 is characterized in that: used Copper Foil applies the one side of homogeneous phase solution and has carried out chemistry or physics roughened.
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| WO2010078821A1 (en) * | 2009-01-06 | 2010-07-15 | 重庆科昌科技有限公司 | Method for preparing subsphaeroidal barium sulfate by sulfuric acid process and its use in copper foil substrate |
| WO2016052316A1 (en) * | 2014-09-30 | 2016-04-07 | 新日鉄住金化学株式会社 | Polyamic acid, polyamide, resin film, and metal-clad laminate |
| WO2018061727A1 (en) * | 2016-09-29 | 2018-04-05 | 新日鉄住金化学株式会社 | Polyimide film, copper-clad laminate, and circuit substrate |
| CN108395534A (en) * | 2018-01-16 | 2018-08-14 | 常州杰铭新材料科技有限公司 | A kind of solubility height and the good bismaleimide performed polymer and its preparation method and application of temperature tolerance |
| CN113121981A (en) * | 2019-12-31 | 2021-07-16 | 广东生益科技股份有限公司 | Resin composition, and prepreg and insulating board using same |
| CN116004183A (en) * | 2023-02-02 | 2023-04-25 | 江苏晶河电子科技有限公司 | High-temperature-resistant adhesive for microelectronic device and preparation method thereof |
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| WO2010078821A1 (en) * | 2009-01-06 | 2010-07-15 | 重庆科昌科技有限公司 | Method for preparing subsphaeroidal barium sulfate by sulfuric acid process and its use in copper foil substrate |
| CN101475200B (en) * | 2009-01-06 | 2012-02-29 | 重庆科昌科技有限公司 | Preparation of subsphaeroidal barium sulfate by sulfuric acid process and use in copper foil substrate |
| WO2016052316A1 (en) * | 2014-09-30 | 2016-04-07 | 新日鉄住金化学株式会社 | Polyamic acid, polyamide, resin film, and metal-clad laminate |
| TWI661005B (en) * | 2014-09-30 | 2019-06-01 | 日商日鐵化學材料股份有限公司 | Polyamic acid, polyimide, resin film and metal-clad laminated board |
| WO2018061727A1 (en) * | 2016-09-29 | 2018-04-05 | 新日鉄住金化学株式会社 | Polyimide film, copper-clad laminate, and circuit substrate |
| JPWO2018061727A1 (en) * | 2016-09-29 | 2019-07-25 | 日鉄ケミカル＆マテリアル株式会社 | Polyimide film, copper clad laminate and circuit board |
| CN108395534A (en) * | 2018-01-16 | 2018-08-14 | 常州杰铭新材料科技有限公司 | A kind of solubility height and the good bismaleimide performed polymer and its preparation method and application of temperature tolerance |
| CN113121981A (en) * | 2019-12-31 | 2021-07-16 | 广东生益科技股份有限公司 | Resin composition, and prepreg and insulating board using same |
| CN116004183A (en) * | 2023-02-02 | 2023-04-25 | 江苏晶河电子科技有限公司 | High-temperature-resistant adhesive for microelectronic device and preparation method thereof |
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Address after: No. 30 Guan Shan Road, Hongshan District, Hubei, Wuhan Patentee after: Huashuo Technology Co., Ltd. Address before: No. 30 Guan Shan Road, Hongshan District, Hubei, Wuhan Patentee before: Hubei Prov. Inst. of Chemistry |
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Denomination of invention: Modified maleimide end-sealed type polyimide resin composite and application thereof Effective date of registration: 20100907 Granted publication date: 20090603 Pledgee: Bank of Hankou, Limited by Share Ltd, Optics Valley branch Pledgor: Huashuo Technology Co., Ltd. Registration number: 2010990000869 |
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Date of cancellation: 20151106 Granted publication date: 20090603 Pledgee: Bank of Hankou Limited by Share Ltd Optics Valley branch Pledgor: Huashuo Technology Co., Ltd. Registration number: 2010990000869 |
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Change date: 20151106 Registration number: 2010990000869 Pledgee after: Bank of Hankou Limited by Share Ltd Optics Valley branch Pledgee before: Bank of Hankou, Limited by Share Ltd, Optics Valley branch |
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Effective date of registration: 20210730 Address after: 436070 light steel plant 2, No. 2 Industrial Zone, Gedian Development Zone, Ezhou City, Hubei Province Patentee after: Huashuo electronic materials (Wuhan) Co.,Ltd. Address before: 430074 No. 30 Guan Shan Road, Hongshan District, Hubei, Wuhan Patentee before: HAISO TECHNOLOGY Co.,Ltd. |