CN118085297A - Cross-linked hybrid polyimide resin for flexible circuit board, preparation method thereof and flexible circuit board - Google Patents
Cross-linked hybrid polyimide resin for flexible circuit board, preparation method thereof and flexible circuit board Download PDFInfo
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- CN118085297A CN118085297A CN202410493409.5A CN202410493409A CN118085297A CN 118085297 A CN118085297 A CN 118085297A CN 202410493409 A CN202410493409 A CN 202410493409A CN 118085297 A CN118085297 A CN 118085297A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 115
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000004642 Polyimide Substances 0.000 claims abstract description 44
- 230000002776 aggregation Effects 0.000 claims abstract description 5
- 238000004220 aggregation Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 74
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 52
- 239000003054 catalyst Substances 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 38
- -1 polysiloxane Polymers 0.000 claims description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 32
- 239000011889 copper foil Substances 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 29
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000003292 glue Substances 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- 238000006317 isomerization reaction Methods 0.000 claims description 23
- 150000004985 diamines Chemical class 0.000 claims description 21
- 229920001296 polysiloxane Polymers 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 14
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 229920005575 poly(amic acid) Polymers 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 6
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 125000001033 ether group Chemical group 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 3
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 claims description 3
- UNIBAJHMJGXVHL-UHFFFAOYSA-N 3-phenylbenzene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C=2C=CC=CC=2)=C1C(O)=O UNIBAJHMJGXVHL-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000010521 absorption reaction Methods 0.000 abstract description 28
- 239000011347 resin Substances 0.000 abstract description 15
- 229920005989 resin Polymers 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000009396 hybridization Methods 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
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- 239000002131 composite material Substances 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000004821 distillation Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 238000005476 soldering Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 239000000376 reactant Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- VZUHQRBBQSLSHS-SSZFMOIBSA-N Isoimide Chemical group C1=CC(Br)=CC=C1\N=C/1C(CCCC2)=C2C(=O)O\1 VZUHQRBBQSLSHS-SSZFMOIBSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
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- 238000010292 electrical insulation Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
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Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a cross-linking hybridization type polyimide resin and a preparation method thereof. The cross-linked hybrid polyimide resin is in an aggregation state structure, and comprises a plurality of polyimide linear main chains and a plurality of flexible molecular chains, wherein the polyimide linear main chains are cross-linked with each other through the flexible molecular chains to form a netlike cross-linked structure. The cross-linked hybridized polyimide resin improves the dissolubility and adhesiveness of resin molecules in a molecular aggregation state, and simultaneously keeps excellent dielectric property and water absorption rate of the resin.
Description
Technical Field
The invention relates to the technical field of polyimide resin, in particular to cross-linked hybrid polyimide resin, a preparation method thereof and a flexible circuit board.
Background
Currently, polyimide is mainly used as a substrate of a flexible circuit board (FPC), and an adhesive is generally coated on the surface of the polyimide substrate, and a multi-layer composite structure of "copper foil/adhesive/polyimide/adhesive/copper foil" is formed by pressing with copper foil through a hot pressing process, thereby obtaining the flexible circuit board (FCCL). The adhesive is mostly epoxy resin, and the thermal expansion coefficient, dielectric property and water absorption difference between the epoxy resin, polyimide and copper foil lead the board making process conditions and the epoxy resin composition formula to be extremely harsh, and limit the requirement of the high-speed high-frequency operation environment on the flexible circuit board (FPC) performance of the multi-component composite flexible circuit board (FCCL).
Along with the popularization of 5G technology and the improvement of 6G technology, the polyimide-based flexible circuit board (FCCL) with a copper foil/polyimide/copper foil composite structure is urgently required in the market field, so that the thickness of the flexible circuit board is reduced, the interconnection density is improved, the multi-layer lamination is realized, and the performance requirement of the high-speed high-frequency operation field on a flexible circuit board (FPC) is met.
Polyimide (PI) resins having an aromatic structure as a main chain are one of the most widely used polymer resins in Flexible Printed Circuits (FPCs) and related product fields, because of their excellent heat resistance, chemical resistance, electrical insulation, chemical resistance, and weather resistance. However, the disadvantages of high brittleness, indissolvable solvent, poor adhesive property and the like make the product have a plurality of challenges in terms of the product forming process and meeting the performance requirements of special occasions.
In the prior art, attempts are made to prepare novel aromatic monomers by introducing flexible groups such as a vinylidene fluoride unit, an ether bond, a sulfonyl group, an alkyl group, a siloxy group and the like into a molecular structure, or to structurally modify polyimide by introducing a flexible chain segment and the like in situ in the process of forming polyamide acid by polycondensation of the monomers, so as to improve the flexibility of a molecular chain, reduce the rigidity density, improve the interaction between resin molecular chains, reduce the cohesive energy density, further improve the solubility of resin, reduce the brittleness and improve the adhesive property to copper foil. However, the local introduction of the flexible groups into the monomer structure can only reflect the steric effect change of the side groups, has small influence on the movement deformation capacity of the main chain structure, and has limited capacity of improving the toughness of the resin; and the flexible chain segment increases with the increase of the length of the molecular chain or the increase of the content of the polar covalent bond, so that the molecular structure is easier to polarize, the dielectric property of the modified polyimide resin is reduced, the water absorption is increased, and the insulating property of the resin is reduced.
Disclosure of Invention
Aiming at the technical problems of high brittleness, difficult solvent dissolution and poor adhesive property of the existing polyimide resin, the invention provides a cross-linked hybrid polyimide resin, a preparation method thereof and a copper-clad plate.
In one aspect, the present invention provides a crosslinked hybrid polyimide resin, wherein the crosslinked hybrid polyimide resin has an aggregated structure, and the crosslinked hybrid polyimide resin comprises a plurality of polyimide linear backbones and a plurality of flexible molecular chains, and the plurality of polyimide linear backbones are crosslinked with each other through the plurality of flexible molecular chains to form a network crosslinked structure.
In the invention, the cross-linked hybridized polyimide resin forms a network structure, reduces the stacking density of molecular chains, damages the arrangement regularity, improves the dissolubility and adhesiveness of resin molecules on the level of molecular aggregation, and simultaneously ensures that the resin keeps excellent dielectric property and water absorption. Solves the problem of void effect caused by thickening of the coating when polyimide resin is coated on the copper foil, and realizes the comprehensive improvement of the resin performance.
Optionally, the polyimide linear main chain has a structure shown in a formula (II-A), the flexible molecular chain is selected from one or more of a carbon chain with a terminal group containing a reactive group, a heteroatom carbon chain with a terminal group containing a reactive group and polysiloxane, the polysiloxane is shown in a formula (II-B),
；
II-A
；
II-B
Wherein R 2 is selected from C1-C5 alkyl or hydrogen; y 1、Y2 is independently selected from oxygen or carbon, x 1、x2 is independently selected from 0 or 1, n is an integer from 50 to 200, m is an integer from 5 to 50, 0<a 1+a2+a3+……+ap < n.
Optionally, n is an integer from 90 to 180, m is an integer from 9 to 36, and n/10< a 1+a2+a3+……+ap <3n/10.
Optionally, the carbon chain with the end group containing a reactive group is selected from at least one of a C10-C40 linear alkane and a branched alkane; the heteroatom carbon chain of which the end group contains a reactive group is selected from at least one of a C10-C50 ether chain and a C10-C50 ester chain.
Optionally, the reactive group is selected from at least one of-NH 2 and-OH.
In another aspect, the present invention also provides a method for preparing the crosslinked hybrid polyimide resin according to any one of the above, comprising the steps of:
Respectively dissolving dicarboxylic anhydride and diamine in a first solvent under a protective atmosphere to obtain a dicarboxylic anhydride solution and a diamine solution; adding the dibasic acid anhydride solution and the diamine solution into a second solvent, and reacting at a first temperature to obtain polyamic acid; adding a first catalyst into the polyamic acid at a second temperature to react to obtain the polyisoimide;
Dissolving the polyisoimide in a third solvent, sequentially adding a compound with a flexible molecular chain and a second catalyst at a third temperature, and reacting to obtain a cross-linked hybrid polyisoimide solution;
adding a solution containing a third catalyst into the cross-linked hybrid polyisoimide solution, reacting at a fourth temperature to obtain an isomerization precursor glue solution of the hybrid cross-linked polyimide, and baking the isomerization precursor glue solution to obtain the cross-linked hybrid polyimide resin.
Optionally, the dibasic acid anhydride is selected from at least one of 3, 4-diphenyl tetracarboxylic dianhydride and 4, 4-diphenyl ether tetracarboxylic anhydride; the diamine is at least one selected from 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl methane and 4,4 '-diamino-3, 3' -dimethylbiphenyl;
The compound with flexible molecular chain is at least one selected from C10-C40 linear alkane and/or branched alkane with a reactive group at the end, C10-C50 ether chain compound with a reactive group at the end, C10-C50 ester chain compound with a reactive group at the end and polysiloxane compound shown in formula (II-B);
The first solvent and the second solvent are respectively and independently selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and toluene; the third solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, toluene, butanone, acetone and carbon tetrachloride;
The first catalyst is selected from one or more of triethylamine/4-dimethylaminopyridine, 2,4, 6-tris (dimethylaminomethyl) phenol/4-dimethylaminopyridine and dicyclohexylcarbodiimide/4-dimethylaminopyridine; the second catalyst is selected from one or more of triethylamine, 4-dimethylaminopyridine and 2,4, 6-tris (dimethylaminomethyl) phenol; the third catalyst is selected from one or more of 4-dimethylaminopyridine, 2,4, 6-tris (dimethylaminomethyl) phenol and 1, 8-diazabicyclo [5.4.0] undec-7-ene.
Optionally, the molar ratio of the diamine to the dicarboxylic anhydride is 0.5-1.5; the molar ratio of the first catalyst to diamine is 0.5-1.5;
the molar ratio of the compound with flexible molecular chain to the polyisoimide is 2.5-30;
the mass of the second catalyst is 0.02-5% of the mass of the polyisoimide;
The mass of the third catalyst is 0.05-5% of the mass of the cross-linked hybrid polyisoimide, and the mass fraction of the third catalyst in the solution containing the third catalyst is 8-10%.
Optionally, the first temperature is-10-30 ℃, the second temperature is 0-45 ℃, and the third temperature is 0-60 ℃; the fourth temperature is 25-30 ℃;
The reaction time for preparing the polyisoimide at the second temperature is 2-12 h;
The reaction time for preparing the cross-linked hybridized polyisoimide solution at the third temperature is 4-48 h;
The baking is gradient heating baking, and the baking conditions are 2-5 h at 90-140 ℃, 3-6 h at 150-200 ℃ and 1-3 h at 220-250 ℃.
On the other hand, the invention also provides a flexible circuit board, which comprises a copper foil and a polyimide film layer, wherein the polyimide film layer is arranged on the copper foil, and is a film formed by any one of the cross-linked hybridized polyimide resin, or is prepared by coating an isomerization precursor glue solution on the surface of the copper foil and baking, and the isomerization precursor glue solution is the isomerization precursor glue solution of the hybridized cross-linked polyimide in the preparation method of the cross-linked hybridized polyimide resin.
In the invention, the isomerization precursor glue solution of the hybridization cross-linked polyimide can be directly coated and formed on the surface of the copper foil, and the polyimide film layer is directly formed after baking, so that the thickness of the flexible circuit board is reduced, the interconnection density is improved, and the multi-layer lamination is realized. The polyimide film layer in the flexible circuit board has the functions of adhesion and insulation, solves the problem that the coating becomes thick and small molecules are released in the imidization process to generate a hole effect, and realizes the comprehensive improvement of the resin performance.
Drawings
FIG. 1 is a schematic view of an aggregate structure of a cross-linked hybrid polyimide resin according to an embodiment of the present invention;
FIG. 2 is an infrared spectrum of a cross-linked hybrid polyimide resin according to an embodiment of the present invention;
FIG. 3 is a FT-IR spectrum of the product of each step in example 2.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In order to illustrate the technical scheme of the invention, the following description is made by specific examples.
In one embodiment of the present invention, a cross-linked hybrid polyimide resin is in an aggregated structure, and the cross-linked hybrid polyimide resin includes a plurality of polyimide linear backbones and a plurality of flexible molecular chains, and the plurality of polyimide linear backbones are cross-linked with each other through the plurality of flexible molecular chains to form a network cross-linked structure.
The aggregate structure of the cross-linked hybrid polyimide resin is shown in fig. 1,Is polyimide linear main chain,/>Is a flexible molecular chain, and a 1、a2、a3、……、ap is the number of the flexible molecular chains.
In this example, the crosslinked hybrid polyimide resin has a network structure, which reduces the stacking density of molecular chains, damages the alignment regularity, improves the solubility and adhesiveness of the resin molecules in the molecular aggregation state, and simultaneously maintains the excellent dielectric properties and water absorption of the resin. Solves the problem of void effect caused by thickening of the coating when polyimide resin is coated on the copper foil, and realizes the comprehensive improvement of the resin performance.
In some embodiments of the present invention, the polyimide linear backbone has a structure represented by formula (II-A), the flexible molecular chain is selected from one or more of a carbon chain having a reactive group at a terminal, a heteroatom carbon chain having a reactive group at a terminal, and a polysiloxane represented by formula (II-B),
；
II-A
；
II-B
Wherein R 2 is selected from C1-C5 alkyl or hydrogen; y 1、Y2 is independently selected from oxygen or carbon, x 1、x2 is independently selected from 0 or 1, n is an integer from 50 to 200, m is an integer from 5 to 50, 0<a 1+a2+a3+……+ap < n.
In a preferred embodiment, the flexible molecular chain is selected from polysiloxanes of formula (II-B). Specifically, the polysiloxane is selected from the group consisting of double-ended primary amino propyl polysiloxanes, wherein the number average molecular weight of the double-ended primary amino propyl polysiloxanes is selected from one or more of 500, 1000, 2000, 3000 and 5000.
In a preferred embodiment, the number average molecular weight of the double-ended primary amino propyl polysiloxane is selected from one or more of 1000, 2000, 3000.
In a preferred embodiment, n is an integer from 90 to 180, m is an integer from 9 to 36, and n/10< a 1+a2+a3+……+ap <3n/10.
In some embodiments of the invention, the carbon chain with the end groups containing a reactive group is selected from at least one of a C10-C40 linear alkane and a branched alkane; the heteroatom carbon chain of which the end group contains a reactive group is selected from at least one of a C10-C50 ether chain and a C10-C50 ester chain.
In a preferred embodiment, the carbon chain with the end groups containing reactive groups is selected from C10-C40 linear alkanes. The heteroatom carbon chain with the end group containing a reactive group is selected from C10-C50 ether chains.
In some embodiments of the invention, the reactive group is selected from at least one of-NH 2 and-OH.
In a preferred embodiment, the reactive group is selected from the group consisting of-NH 2.
In another aspect, an embodiment of the present invention also provides a method for preparing the crosslinked hybrid polyimide resin according to any one of the above, comprising the steps of:
Respectively dissolving dicarboxylic anhydride and diamine in a first solvent under a protective atmosphere to obtain a dicarboxylic anhydride solution and a diamine solution; and adding the dibasic acid anhydride solution and the diamine solution into a second solvent, and reacting at a first temperature to obtain polyamic acid, wherein the reaction time involved in the preparation stage of the polyamic acid is determined by a method for measuring the actual acid value of a reaction system. The measurement method adopts potassium hydroxide titration method. Adding a first catalyst into the polyamic acid at a second temperature to react to obtain the polyisoimide; specifically, a first catalyst is added into the polyamic acid at a second temperature for constant temperature stirring until the solution is turbid, and stirring reaction is continued for a certain time to obtain a polyisoimide suspension. After the reaction is finished, the reaction product is subjected to vacuum suction filtration by using a Buchner funnel, and solid particles are removed to obtain a pale yellow transparent solution, namely the polyisoimide. Specifically, the pale yellow transparent solution is transferred to a rotary evaporator, the first solvent is recovered by reduced pressure distillation, after the distillation is finished, 5 to 20 times (volume ratio) of isopropanol is added to the reduced pressure distillation residue at room temperature, and the mixture is stirred, dispersed and washed 3 to 8 times at a reflux temperature, so that white needle-like crystals are obtained. The protective atmosphere is selected from nitrogen or argon.
Dissolving the polyisoimide in a third solvent, sequentially adding a compound with a flexible molecular chain and a second catalyst at a third temperature, and reacting to obtain a cross-linked hybrid polyisoimide solution; specifically, the second catalyst is dissolved in the third solvent to prepare a solution to be added to the polyisoimide solution, and the second catalyst is prepared into a catalyst solution with a solid content of 10%. The compound having a flexible molecular chain was added dropwise to the polyisoimide solution using a constant pressure dropping funnel. Finally, the cross-linked hybridized polyisoimide solution obtained by the reaction is distilled and concentrated to a solution with 30 to 50 percent of solid content under reduced pressure for the next reaction.
Adding a solution containing a third catalyst into the cross-linked hybrid polyisoimide solution, reacting at a fourth temperature to obtain an isomerization precursor glue solution of the hybrid cross-linked polyimide, and baking the isomerization precursor glue solution to obtain the cross-linked hybrid polyimide resin.
In this embodiment, the preparation method of the crosslinked hybrid polyimide resin includes three steps of preparing the polyisoimide, preparing the crosslinked hybrid polyisoimide, isomerizing the hybrid polyisoimide to form the crosslinked polyimide, and in the step of isomerizing the hybrid polyisoimide to form the crosslinked polyimide, the crosslinked polyimide can be directly coated on a copper foil to form a polyimide film on the surface of the copper foil after baking, so that the thickness of a flexible circuit board is reduced, the interconnection density is improved, and the multilayer lamination is realized.
In some embodiments of the invention, the isomerized precursor dope is poured onto a polytetrafluoroethylene plate, and cast into a film;
And (3) placing the polytetrafluoroethylene flat plate with the isomerism precursor glue solution in an oven with a program temperature control, baking until the solvent is completely volatilized, and drawing the surface. And (3) heating the oven to different temperature stages according to a heating program, and keeping the oven at constant temperature for a certain time.
Taking out the polytetrafluoroethylene flat plate from the oven, and soaking in boiling water until the film falls off from the surface of the polytetrafluoroethylene flat plate. And (3) putting the film into a baking oven at 100-120 ℃ and drying the moisture to obtain the cross-linked hybrid polyimide resin film.
In some embodiments of the invention, the dibasic anhydride is selected from at least one of 3, 4-biphenyltetracarboxylic dianhydride and 4, 4-biphenylether tetracarboxylic anhydride. The diamine is at least one selected from 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl methane and 4,4 '-diamino-3, 3' -dimethylbiphenyl.
The compound having a flexible molecular chain is at least one selected from the group consisting of C10-C40 linear and/or branched alkanes having a reactive group at the end, C10-C50 ether chain compounds having a reactive group at the end, C10-C50 ester chain compounds having a reactive group at the end, and silicone compounds represented by the formula (II-B).
The first solvent and the second solvent are respectively and independently selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and toluene. The third solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, toluene, butanone, acetone and carbon tetrachloride.
The first catalyst is selected from one or more of triethylamine/4-dimethylaminopyridine, 2,4, 6-tris (dimethylaminomethyl) phenol/4-dimethylaminopyridine and dicyclohexylcarbodiimide/4-dimethylaminopyridine. Wherein, the 4-dimethylaminopyridine plays a role of a dehydrating agent. The second catalyst is selected from one or more of triethylamine, 4-dimethylaminopyridine and 2,4, 6-tris (dimethylaminomethyl) phenol. The third catalyst is selected from one or more of 4-dimethylaminopyridine, 2,4, 6-tris (dimethylaminomethyl) phenol and 1, 8-diazabicyclo [5.4.0] undec-7-ene.
In a preferred embodiment, the dianhydride is selected from 4, 4-diphenyl ether tetracarboxylic acid anhydride and the diamine is selected from 4,4' -diaminodiphenyl ether.
The first solvent is selected from N-methyl pyrrolidone, the second solvent is selected from toluene, the volume ratio of N-methyl pyrrolidone to toluene is 20:1-3:1, preferably the volume ratio of N-methyl pyrrolidone to toluene is 10:1-4:1. The third solvent is selected from butanone and toluene, the toluene dosage is 0.1-0.8 times of butanone dosage, preferably 0.2-0.4 times
The first catalyst is selected from dicyclohexylcarbodiimide/4-dimethylaminopyridine. The second catalyst is selected from 4-dimethylaminopyridine, 2,4, 6-tris (dimethylaminomethyl) phenol. The third catalyst is selected from 4-dimethylaminopyridine.
In some embodiments of the invention, the solids content of the reactants and products involved in the preparation of the polyisoimide is controlled between 2 and 30%, preferably between 5 and 20%.
The solid content of the reactants and products involved in the preparation of the crosslinked hybrid polyisoimide is controlled between 5 and 30%, preferably between 10 and 20%.
In some embodiments of the invention, the molar ratio of the diamine to the dicarboxylic anhydride is 0.5 to 1.5. The molar ratio of the first catalyst to diamine is 0.5-1.5.
The molar ratio of the compound with flexible molecular chain to the polyisoimide is 2.5-30.
The mass of the second catalyst is 0.02-5% of the mass of the polyisoimide.
The mass of the third catalyst is 0.05-5% of the mass of the cross-linked hybrid polyisoimide, and the mass fraction of the third catalyst in the solution containing the third catalyst is 8-10%.
In a preferred embodiment, the molar ratio of the diamine to the dicarboxylic anhydride is 0.8 to 1.2. The molar ratio of the first catalyst to diamine is 0.9-1.05.
The molar ratio of the compound having a flexible molecular chain to the polyisoimide is 4.5 to 25.
The mass of the second catalyst is 0.05-3% of the mass of the polyisoimide.
The mass of the third catalyst is 1-3% of that of the cross-linked hybridized polyisoimide, and the mass fraction of the third catalyst in the solution containing the third catalyst is 10%.
In some embodiments of the invention, the first temperature is-10 to 30 ℃, the second temperature is 0 to 45 ℃, and the third temperature is 0 to 60 ℃. The fourth temperature is 25-30 ℃.
The reaction time for preparing the polyisoimide at the second temperature is 2-12 h.
The reaction time for preparing the cross-linked hybridized polyisoimide solution at the third temperature is 4-48 h.
The baking is gradient heating baking, and the baking conditions are 2-5 h at 90-140 ℃, 3-6 h at 150-200 ℃ and 1-3 h at 220-250 ℃.
In a preferred embodiment, the first temperature is 0 to 25 ℃, the second temperature is 15 to 30 ℃, and the third temperature is 20 to 50 ℃.
The reaction time for preparing the polyisoimide at the second temperature is 4-8 h.
And the reaction time for preparing the cross-linked hybridized polyisoimide solution at the third temperature is 8-24 h.
On the other hand, an embodiment of the present invention further provides a flexible circuit board, including a copper foil and a polyimide film layer, where the polyimide film layer is disposed on the copper foil, and the polyimide film layer is a film formed by the crosslinked hybrid polyimide resin according to any one of the above embodiments, or the polyimide film layer is prepared by coating an isomerization precursor glue solution on a surface of the copper foil and baking the coated film, and the isomerization precursor glue solution is the isomerization precursor glue solution of the hybrid crosslinked polyimide in the preparation method of the crosslinked hybrid polyimide resin according to any one of the above embodiments.
In the embodiment, the polyimide film layer in the flexible circuit board has the functions of adhesion and insulation, solves the problem that the coating becomes thick and small molecules are released in the imidization process to generate a hole effect, and realizes the comprehensive improvement of the resin performance.
The invention is further illustrated by the following examples.
Example 1
In this example, 3, 4-biphenyltetracarboxylic dianhydride and 4,4 '-diaminodiphenyl ether were respectively dispersed and dissolved in N-methylpyrrolidone (NMP), toluene was added to the flask, a3, 4-biphenyltetracarboxylic dianhydride solution and a4, 4' -diaminodiphenyl ether solution were added to the flask, nitrogen was introduced, stirring was performed at a constant temperature within 0 to 30℃and the actual acid value of the reaction system was measured every 1 hour until the theoretical acid value was reached, and the reaction was stopped to obtain polyamic acid. The molar ratio of 3, 4-diphenyl tetracarboxylic dianhydride to 4,4' -diaminodiphenyl ether is 0.75,
And (3) regulating the system temperature in the flask to 0-25 ℃, adding dicyclohexylcarbodiimide/4-dimethylaminopyridine, stirring at constant temperature until the solution is turbid, and continuing stirring reaction to obtain the polyisoimide suspension. After the reaction was completed, the reaction product was suction-filtered under reduced pressure using a buchner funnel to remove solid particles, thereby obtaining a pale yellow transparent solution. Transferring the solution to a rotary evaporator, recovering the first solvent by reduced pressure distillation, adding 5-20 times (volume ratio) of isopropanol into the reduced pressure distillation residue at room temperature after the distillation is finished, stirring, dispersing and washing for 3-8 times at reflux temperature to obtain white needle-like crystals, namely the polyisoimide. The molar ratio of dicyclohexylcarbodiimide and 4-dimethylaminopyridine to 4,4' -diaminodiphenyl ether, respectively, was 0.75.
Adding the polyisoimide into a flask, adding a mixed solvent of butanone and toluene into the flask, introducing nitrogen, heating to 20-50 ℃, keeping constant temperature stirring, and dropwise adding the double-end primary amino propyl polysiloxane with the formula dosage into a stirring system by using a constant pressure dropping funnel. After the dripping is completed, stirring at constant temperature until the mixture is uniformly dispersed. Adding 4-dimethylaminopyridine and 2,4, 6-tris (dimethylaminomethyl) phenol solution into the mixed system, and stirring at constant temperature to obtain a light yellow viscous solution, namely an organosilicon modified polyisoimide solution. The molar ratio of the double-ended primary amino propyl polysiloxane to the polyisoimide is 2.5. The total amount of 4-dimethylaminopyridine, 2,4, 6-tris (dimethylaminomethyl) phenol was 3% of the mass of the silicone modified polyisoimide.
Adding an organosilicon modified polyisoimide with a certain mass into a flask, adding a 4-dimethylaminopyridine solution with the concentration of 10%, introducing nitrogen, stirring at a constant temperature of 25 ℃ to obtain an isomerization precursor solution of the organosilicon modified polyimide, pouring the isomerization precursor solution onto a polytetrafluoroethylene flat plate, and casting to form a film. The mass of the 4-dimethylaminopyridine is 1% of that of the organosilicon modified polyisoimide.
And (3) placing the polytetrafluoroethylene flat plate with the isomerism precursor glue solution in an oven with a program temperature control, baking until the solvent is completely volatilized, and drawing the surface. According to the conditions of 90-140 ℃ for 2-5 h, 150-200 ℃ for 3-6 h and 220-250 ℃ for 1-3 h. And heating up, namely heating the oven to different temperature stages, and keeping the oven at constant temperature for a certain time.
Taking out the polytetrafluoroethylene flat plate from the oven, and soaking in boiling water until the film falls off from the surface of the polytetrafluoroethylene flat plate. And (3) putting the film into a baking oven at 100-120 ℃ and drying the moisture to obtain the cross-linked hybrid polyimide resin film.
In FIG. 2, the absorption peaks at 498cm -1、802cm-1 and 1013cm -1 representAbsorption peaks of-Si-O-Si-, -O-and-C-Si-in the group; the absorption peak at 1237cm -1 represents/>Radicals/>The absorption peak of medium-C-N-, the absorption peak at 1567cm -1 represents/>Absorption peak of-c=n-in the group. Absorption peaks at 1718cm -1 and at 1782cm -1 represent/>, in the ring-opened (silicone modified) product of the isoimide ring, in the polyimide ring formed by isomerizationIs not shown; the absorption peak at 1803cm -1 represents a polyisoimideIn structure/>Is not shown; the absorption peaks at 2857cm -1、2940cm-1 and 1367cm -1 represent the absorption peak of the-CH 2-、-CH3 group, with the absorption peak at 1367cm -1 being/>An absorption peak of-CH 3 in the group structure; the absorption peaks at 3322cm -1 and 1606cm -1 represent the absorption peaks for the-NH 2, -NH-groups.
Comparing the infrared spectrograms of the products of different stages (taking the infrared spectrum data of the polyamic acid as a reference) and finding that the infrared spectrograms of the polyisoimide show the representative polyisoimide at 1803cm -1 and 1567cm -1 In structure/>、/>Is located at 1718cm -1 and represents/>, in the uncyclic polyamide structureA red shift occurs and the absorption peak is significantly reduced, which indicates that the polyamic acid forms a loop to form a polyisoimide.
In the infrared spectrum of the silicone-modified polyisoimide, absorption peaks at 498cm -1、802cm-1 and 1013cm -1 are representedAbsorption peaks of-Si-O-Si-, -O-and-C-Si-in the group, and a position at 1803cm -1 and 1567cm -1 represents a polyisoimide/>In structure/>、/>The absorption peak of (a) disappeared and reappeared at 1718cm -1 and at 1782cm -1 to represent the product of ring opening of the isopolyimide ring (silicone modified), the/>, in the polyimide ring formed by isomerizationThe results indicate that the partially opened polyisoimide ring forms a silicone-modified polyamide with a small amount of the polyimide ring formed by isomerization of the polyisoimide ring under the action of the amino-organosiloxane.
In the infrared spectrum of the organosilicon modified polyimide, except for-Si-O-Si-in the organosilicon structure outside the absorption peak of-O-and-C-Si-, located at 1782cm -1 represents a polyimide ringIs strong and no/>, representing the polyisoimide ring structure, at 1567cm -1 and 1803cm -1 appears、/>Is not shown in the figure).
The above analysis results show that the final product prepared is a silicone modified polyimide resin.
The reaction process is shown in a formula III:
；
formula III
Example 2
In this example, the detailed implementation is similar to example 1, except that: instead of the double-ended primary aminopropyl polysiloxane, a linear alkane with a terminal group containing-NH 2 was used.
Example 3
In this example, the detailed implementation is similar to example 1, except that: instead of the double-ended primary aminopropyl polysiloxane, an ether chain compound whose end groups contain-NH 2 was used.
Example 4
In this example, the detailed implementation is similar to example 1, except that: the first catalyst is selected from triethylamine/4-dimethylaminopyridine. The second catalyst is selected from triethylamine. The third catalyst is selected from 2,4, 6-tris (dimethylaminomethyl) phenol.
Example 5
In this example, the detailed implementation is similar to example 1, except that: the molar ratio of 3, 4-diphenyl tetracarboxylic dianhydride to 4,4' -diaminodiphenyl ether was 1.1, and the molar ratio of double-ended primary aminopropyl polysiloxane to polyisoimide was 30.
Performance testing
The crosslinked hybrid polyimide resin films of examples 1 to 3 were subjected to temperature resistance, dielectric properties, and mechanical properties, and the test results obtained were filled in Table 1. The testing method comprises the following steps:
Temperature resistance
1) Initial thermal decomposition temperature
Initial thermal decomposition temperature of film) The test was performed on a TGA55 thermogravimetric analyzer. The test condition is N 2 atmosphere, the flow rate is 25mL/min, the heating rate is 20 ℃/min, and the temperature range is 25-800 ℃.
2) Glass transition temperature (Tg)
The glass transition temperature (Tg) of the films was measured on a TA Q800 dynamic mechanical property tester. Test conditions: the test frequency is 1Hz, the heating rate is 2 ℃/min, and the temperature range is 25 ℃ to 400 ℃. Sample size: 70 mm. Times.10 mm. Times.0.05 mm.
Dielectric property test
The dielectric properties were tested on an instrument model vector network analyzer-cylindrical resonator. Test conditions: the test frequency was 10GHz. Sample size: 70mm by 0.05mm.
Mechanical property test
The mechanical property test of the film is carried out on a Shenzhen new think carefully CMT-6503 microcomputer control electronic universal tensile tester for testing the tensile property of the film. Test temperature was room temperature, sample size: 100mm×10mm×0.05mm, loading speed: 2mm/min.
Water absorption rate
The water absorption is measured by a gravimetric method. Test conditions and methods:
Sample size: 70mm by 0.05mm;
The testing method comprises the following steps:
1) Placing the sample in an oven at 120 ℃ for constant temperature drying for 2 hours, and placing the sample in a vacuum dryer for cooling for 0.5 hour;
2) The sample was taken out, weighed with an analytical balance (precision 0.1 mg) and noted as W 0;
3) Placing the sample in a constant-temperature water bath kettle at 100 ℃ and soaking for 24 hours;
4) The sample was taken out, the surface moisture was sucked up with filter paper, and rapidly weighed (precision 0.1 mg) with an analytical balance, designated as W 1;
5) Using the formula: And calculating to obtain the water absorption.
Coating the isomerism precursor glue solution of the hybridized cross-linked polyimide in the embodiment 1-3 on the surface of the copper foil, drying the solvent, and additionally cutting two copper foils with the same area outside and attaching the copper foils coated with the glue solution to form a sandwich structure. The flexible circuit board with the cross-linking hybridization polyimide/copper foil composite structure is prepared according to the baking conditions of 2-5 h at 90-140 ℃, 3-6 h at 150-200 ℃ and 1-3h at 220-250 ℃. Performance testing was performed on the prepared flexible circuit board and the comparative sample, and the obtained test results were filled in table 2.
In comparative sample 1, the polyimide resin in the polyimide film layer was an epoxy-based polyimide resin, and the trade name was BT25.
In comparative sample 2, the polyimide resin in the polyimide film layer was an epoxy-based polyimide resin, and the trade name was SLF.
The testing method comprises the following steps:
tin soldering resistance test
The copper foil coated with the isomerism precursor glue solution of the hybridization cross-linked polyimide is baked for 2 to 5 hours at the temperature of between 90 and 140 ℃,3 to 6 hours at the temperature of between 150 and 200 ℃ and 1 to 3 hours at the temperature of between 220 and 250 ℃ to prepare the copper foil/cross-linked hybridization polyimide/copper foil composite material. And (3) placing the composite material into soldering tin liquid with different temperatures (300+/-20 ℃) for 10 seconds, and observing the foaming or layering condition of the composite material at different temperatures to determine the soldering resistance of the material.
Peel force test
The peel force test of the composite material is carried out by referring to GBT1457-2005 sandwich structure roller peel strength test method, and the loading direction is as follows: along the copper foil surface 90 DEG, the loading speed is 2mm/min.
TABLE 1
As can be seen from the test results in table 1 and table 2, the crosslinked hybrid polyimide resin films prepared in example 1, example 2 and example 3 all have excellent properties such as high temperature resistance, high tensile strength and elongation, low dielectric constant and dielectric loss, low moisture absorption, high adhesion (copper foil) and high soldering temperature resistance; compared with the products BT-25 and SLF of the same type, the cross-linked hybrid polyimide resin film has more excellent peel strength (copper foil), soldering temperature resistance, lower dielectric constant and equivalent dielectric loss. In addition, the hybridized cross-linked polyimide is directly coated and formed on the surface of the copper foil at 25 ℃ by adopting an isomerization precursor glue solution (hybridized cross-linked polyisoimide), and a hybridized cross-linked polyimide glue layer is formed by utilizing a heating isomerization effect (without small molecule products), so that the hybridized cross-linked polyimide glue layer directly replaces a polyimide resin carrier film and plays a role in electric insulation. The thickness of flexible circuit board can be effectually reduced, interconnection density is improved, realizes the laminating of multilayer, promotes the work efficiency of multilayer FPC panel.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting. Although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some of the technical features thereof can be replaced by equivalents. Such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention, and are intended to be included in the scope of the present invention.
Claims (10)
1. The cross-linked hybrid polyimide resin is characterized in that the cross-linked hybrid polyimide resin is in an aggregation state structure, and comprises a plurality of polyimide linear main chains and a plurality of flexible molecular chains, wherein the polyimide linear main chains are cross-linked with each other through the flexible molecular chains to form a reticular cross-linked structure.
2. The crosslinked hybrid polyimide resin according to claim 1, wherein the polyimide linear main chain has a structure represented by the formula (II-A), the flexible molecular chain is selected from one or more of a carbon chain having a reactive group at a terminal, a heteroatom carbon chain having a reactive group at a terminal, and a polysiloxane represented by the formula (II-B),
；
II-A
；
II-B
Wherein R 2 is selected from C1-C5 alkyl or hydrogen; y 1、Y2 is independently selected from oxygen or carbon, x 1、x2 is independently selected from 0 or 1, n is an integer from 50 to 200, m is an integer from 5 to 50, 0 < a 1+a2+a3+……+ap < n.
3. The crosslinked hybrid polyimide resin according to claim 2, wherein n is an integer of 90 to 180, m is an integer of 9 to 36, and n/10 < a 1+a2+a3+……+ap <3n/10.
4. The crosslinked hybrid polyimide resin according to claim 2, wherein the carbon chain having a reactive group at the end group is selected from at least one of C10-C40 linear alkane and branched alkane; the heteroatom carbon chain of which the end group contains a reactive group is selected from at least one of a C10-C50 ether chain and a C10-C50 ester chain.
5. The crosslinked hybrid polyimide resin according to claim 2, wherein the reactive group is selected from at least one of-NH 2 and-OH.
6. A method for producing the crosslinked hybrid polyimide resin according to any one of claims 1 to 5, comprising the steps of:
Respectively dissolving dicarboxylic anhydride and diamine in a first solvent under a protective atmosphere to obtain a dicarboxylic anhydride solution and a diamine solution; adding the dibasic acid anhydride solution and the diamine solution into a second solvent, and reacting at a first temperature to obtain polyamic acid; adding a first catalyst into the polyamic acid at a second temperature to react to obtain the polyisoimide;
Dissolving the polyisoimide in a third solvent, sequentially adding a compound with a flexible molecular chain and a second catalyst at a third temperature, and reacting to obtain a cross-linked hybrid polyisoimide solution;
adding a solution containing a third catalyst into the cross-linked hybrid polyisoimide solution, reacting at a fourth temperature to obtain an isomerization precursor glue solution of the hybrid cross-linked polyimide, and baking the isomerization precursor glue solution to obtain the cross-linked hybrid polyimide resin.
7. The method for producing a crosslinked hybrid polyimide resin according to claim 6, wherein the dibasic acid anhydride is at least one selected from the group consisting of 3, 4-biphenyltetracarboxylic dianhydride and 4, 4-biphenylether tetracarboxylic anhydride; the diamine is at least one selected from 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl methane and 4,4 '-diamino-3, 3' -dimethylbiphenyl;
The compound with flexible molecular chain is at least one selected from C10-C40 linear alkane and/or branched alkane with a reactive group at the end, C10-C50 ether chain compound with a reactive group at the end, C10-C50 ester chain compound with a reactive group at the end and polysiloxane compound shown in formula (II-B);
The first solvent and the second solvent are respectively and independently selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and toluene; the third solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, toluene, butanone, acetone and carbon tetrachloride;
The first catalyst is selected from one or more of triethylamine/4-dimethylaminopyridine, 2,4, 6-tris (dimethylaminomethyl) phenol/4-dimethylaminopyridine and dicyclohexylcarbodiimide/4-dimethylaminopyridine; the second catalyst is selected from one or more of triethylamine, 4-dimethylaminopyridine and 2,4, 6-tris (dimethylaminomethyl) phenol; the third catalyst is selected from one or more of 4-dimethylaminopyridine, 2,4, 6-tris (dimethylaminomethyl) phenol and 1, 8-diazabicyclo [5.4.0] undec-7-ene.
8. The method for producing a crosslinked hybrid polyimide resin according to claim 6, wherein the molar ratio of the diamine to the dibasic acid anhydride is 0.5 to 1.5; the molar ratio of the first catalyst to diamine is 0.5-1.5;
the molar ratio of the compound with flexible molecular chain to the polyisoimide is 2.5-30;
the mass of the second catalyst is 0.02-5% of the mass of the polyisoimide;
The mass of the third catalyst is 0.05-5% of the mass of the cross-linked hybrid polyisoimide, and the mass fraction of the third catalyst in the solution containing the third catalyst is 8-10%.
9. The method for preparing a cross-linked hybrid polyimide resin according to claim 6, wherein the first temperature is-10 to 30 ℃, the second temperature is 0 to 45 ℃, and the third temperature is 0 to 60 ℃; the fourth temperature is 25-30 ℃;
The reaction time for preparing the polyisoimide at the second temperature is 2-12 h;
The reaction time for preparing the cross-linked hybridized polyisoimide solution at the third temperature is 4-48 h;
The baking is gradient heating baking, and the baking conditions are 2-5 h at 90-140 ℃, 3-6 h at 150-200 ℃ and 1-3 h at 220-250 ℃.
10. A flexible circuit board, which is characterized by comprising a copper foil and a polyimide film layer, wherein the polyimide film layer is arranged on the copper foil, the polyimide film layer is a film formed by the cross-linked hybridized polyimide resin according to any one of claims 1-5, or the polyimide film layer is prepared by coating an isomerization precursor glue solution on the surface of the copper foil and baking, and the isomerization precursor glue solution is the isomerization precursor glue solution of the hybridized cross-linked polyimide in the preparation method of the cross-linked hybridized polyimide resin according to any one of claims 6-9.
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