CN101260188B - Soluble polyimide resin and composition thereof, composite material and flexible circuit board using the resin or composition thereof - Google Patents
Soluble polyimide resin and composition thereof, composite material and flexible circuit board using the resin or composition thereof Download PDFInfo
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- CN101260188B CN101260188B CN2007101918171A CN200710191817A CN101260188B CN 101260188 B CN101260188 B CN 101260188B CN 2007101918171 A CN2007101918171 A CN 2007101918171A CN 200710191817 A CN200710191817 A CN 200710191817A CN 101260188 B CN101260188 B CN 101260188B
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Abstract
The invention discloses a soluble polyimide resin which not only has excellent cohesiveness on metal foils, but also has the necessary high mechanical strength, heat resistance and dimensional stability as a support film. The polyimide resin, which can be directly formed into a film on metal foils through a flow casting method, can be used to produce a flexible circuit board. Meanwhile, the invention also provides a compound containing the polyimide resin, a metal foil composite material adopting the polyimide resin or complex as well as a flexible circuit board adopting the metal foil composite material.
Description
Technical field
The present invention relates to a kind ofly can and comprise the composition of this resin by the film forming soluble polyimide resin of casting method, and a kind of by with described resin or the composition metal-foil composite that casting film-forming makes on tinsels such as Copper Foil, and a kind of flexible electric circuit board that uses this metal-foil composite.
Background technology
Polyimide resin is insoluble in organic solvent, and therefore, generally first synthesizing polyamides acid in polar solvent is heated again, the dehydration closed-loop reaction takes place, synthesis of polyimides under the effect of chemical agent.Can carry out the casting method film forming to polyamic acid by this method, but after film forming, also must could obtain polyimide resin film through pyroprocessing.In recent years, the polyimide resin of prior art production solubility (referring to patent: the spy opens flat 10-195402, the spy opens 2005-336425), it is used to the heat-resistant glue field.
Disclosed soluble polyamide imide resin only is used for bonding Kapton and Copper Foil in above-mentioned patent, and the Kapton that is posted within on the Copper Foil must possess excellent mechanical intensity, thermotolerance and dimensional stability, therefore can only prepare by method for distinguishing.If adopt with the direct casting film-forming on Copper Foil of soluble polyimide resin, then not only need this polyimide resin to have good cementability, also need it to possess as the necessary good mechanical strength of support membrane, thermotolerance and dimensional stability etc. to Copper Foil.And disclosed soluble polyimide resin does not possess above-mentioned characteristic in the prior art.
Summary of the invention
Based on above-mentioned present situation, the object of the present invention is to provide a kind of soluble polyimide resin, this resin not only has the good cementability to tinsel, also have simultaneously as the necessary good mechanical strength of support membrane, thermotolerance and dimensional stability, therefore can directly on tinsel, carry out casting film-forming and be used to make flexible electric circuit board; The present invention provides a kind of composition that comprises this polyimide resin simultaneously, and has used the metal-foil composite of described polyimide resin or molectron, and has used the flexible electric circuit board of this metal-foil composite.
To achieve the above object of the invention, the present invention takes following technical scheme:
Scheme one: a kind of soluble polyimide resin, comprise quaternary carboxylic end group and diamine end group, the tensile strength after its cast film forming is greater than 50N (30 μ m are thick, and 20mm is wide), and thermal linear expansion coefficient is less than 4.0 * 10
-5℃
-1The described quaternary carboxylic end group of 50～100mol% is an at least a end group in the following quaternary carboxylic acid: 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-diphenyl sulfone tetraformic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic, 3,3 ', 4,4 '-diphenyl ether tetraformic, trimellitic acid 1,2-anhydride glycol ester; The described diamine end group of 50～100mol% is an end group at least a in the following diamine: Ursol D, 3,3-dimethyl-4,4-benzidine, 1,5-naphthylene diamine, 2,6-naphthylene diamine.
Scheme two: a kind of composition that comprises scheme one described soluble polyimide resin, said composition comprises 100 parts of described soluble polyimide resins, 10～100 parts of thermosetting resins.Described soluble polyimide resin comprises quaternary carboxylic end group and diamine end group, and the tensile strength after its cast film forming is greater than 50N (30 μ m are thick, and 20mm is wide), and thermal linear expansion coefficient is less than 4.0 * 10
-5℃
-1The described quaternary carboxylic end group of 50～100mol% is an at least a end group in the following quaternary carboxylic acid: 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-diphenyl sulfone tetraformic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic, 3,3 ', 4,4 '-diphenyl ether tetraformic, trimellitic acid 1,2-anhydride glycol ester; The described diamine end group of 50～100mol% is an end group at least a in the following diamine: Ursol D, 3,3-dimethyl-4,4-benzidine, 1,5-naphthylene diamine, 2,6-naphthylene diamine.
Scheme three: a kind of matrix material that uses scheme one described soluble polyimide resin, this matrix material comprises tinsel and the soluble polyimide resin that is coated on this metal foil surface, this soluble polyimide resin comprises quaternary carboxylic end group and diamine end group, (30 μ m are thick greater than 50N for tensile strength after its cast film forming, 20mm is wide), thermal linear expansion coefficient is less than 4.0 * 10
-5℃
-1The described quaternary carboxylic end group of 50～100mol% is an at least a end group in the following quaternary carboxylic acid: 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-diphenyl sulfone tetraformic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic, 3,3 ', 4,4 '-diphenyl ether tetraformic, trimellitic acid 1,2-anhydride glycol ester; The described diamine end group of 50～100mol% is an end group at least a in the following diamine: Ursol D, 3,3-dimethyl-4,4-benzidine, 1,5-naphthylene diamine, 2,6-naphthylene diamine.
Scheme four: a kind of matrix material that uses scheme two described compositions, this matrix material comprise tinsel and are coated in the composition of the soluble polyimide resin on this metal foil surface; Said composition comprises 100 parts of soluble polyimide resins, 10～100 parts of thermosetting resins.Described soluble polyimide resin comprises quaternary carboxylic end group and diamine end group, and the tensile strength after its cast film forming is greater than 50N (30 μ m are thick, and 20mm is wide), and thermal linear expansion coefficient is less than 4.0 * 10
-5℃
-1The described quaternary carboxylic end group of 50～100mol% is an at least a end group in the following quaternary carboxylic acid: 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-diphenyl sulfone tetraformic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic, 3,3 ', 4,4 '-diphenyl ether tetraformic, trimellitic acid 1,2-anhydride glycol ester; The described diamine end group of 50～100mol% is an end group at least a in the following diamine: Ursol D, 3,3-dimethyl-4,4-benzidine, 1,5-naphthylene diamine, 2,6-naphthylene diamine
Scheme five: a kind of flexible electric circuit board that uses scheme three described matrix materials, at least a portion of this flexible electric circuit board is the matrix material of soluble polyimide resin, and this matrix material comprises tinsel and the soluble polyimide resin that is coated on this metal foil surface.Described soluble polyimide resin comprises quaternary carboxylic end group and diamine end group, and the tensile strength after its cast film forming is greater than 50N (30 μ m are thick, and 20mm is wide), and thermal linear expansion coefficient is less than 4.0 * 10
-5℃
-1The described quaternary carboxylic end group of 50～100mol% is an at least a end group in the following quaternary carboxylic acid: 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-diphenyl sulfone tetraformic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic, 3,3 ', 4,4 '-diphenyl ether tetraformic, trimellitic acid 1,2-anhydride glycol ester; The described diamine end group of 50～100mol% is an end group at least a in the following diamine: Ursol D, 3,3-dimethyl-4,4-benzidine, 1,5-naphthylene diamine, 2,6-naphthylene diamine.
Scheme six: a kind of flexible electric circuit board that uses scheme four described matrix materials, at least a portion of this flexible electric circuit board is the matrix material of the composition of soluble polyimide resin, and this matrix material comprises tinsel and is coated in the composition of the soluble polyimide resin on this metal foil surface.Described composition comprises 100 parts of soluble polyimide resins, 10～100 parts of thermosetting resins; Described soluble polyimide resin comprises quaternary carboxylic end group and diamine end group, and the tensile strength after its cast film forming is greater than 50N (30 μ m are thick, and 20mm is wide), and thermal linear expansion coefficient is less than 4.0 * 10
-5℃
-1The described quaternary carboxylic end group of 50～100mol% is an at least a end group in the following quaternary carboxylic acid: 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-diphenyl sulfone tetraformic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic, 3,3 ', 4,4 '-diphenyl ether tetraformic, trimellitic acid 1,2-anhydride glycol ester; The described diamine end group of 50～100mol% is an end group at least a in the following diamine: Ursol D, 3,3-dimethyl-4,4-benzidine, 1,5-naphthylene diamine, 2,6-naphthylene diamine.
Can directly be dissolved in organic solvent according to polyimide resin of the invention process, need not to make it imidization with the state dissolving reheat of polyamic acid.Therefore can directly its solution curtain coating on tinsel be coated with, and then drying and forming-film.
Not only have good bonding according to polyimide resin of the invention process, have good physical strength, thermotolerance and dimensional stability as support membrane simultaneously tinsel.Metal-foil composite according to scheme three and scheme four enforcements can be directly used in the manufacturing flexible electric circuit board, and its processibility and use properties are all very good.
Embodiment
Comprise quaternary carboxylic end group and diamine end group according to soluble polyimide resin of the invention process, wherein, the described quaternary carboxylic end group of 50～100mol% is an at least a end group in the following quaternary carboxylic acid: 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-diphenyl sulfone tetraformic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic, 3,3 ', 4,4 '-diphenyl ether tetraformic, trimellitic acid 1,2-anhydride glycol ester; The described diamine end group of 50～100mol% is an end group at least a in the following diamine: Ursol D, 3,3-dimethyl-4,4-benzidine, 1,5-naphthylene diamine, 2,6-naphthylene diamine.
For for simplicity, below all directly with the quaternary carboxylic acid that forms the quaternary carboxylic end group itself represent quaternary carboxylic end group in the polyimide resin composition, itself represent the amine-terminated composition of binary in the polyimide resin with the amine-terminated diamine of formation binary.
Select at least aly from described various quaternary carboxylic acids, its content need account for 50～100mol% of all quaternary carboxylic acids.If this molar percentage less than 50mol%, then is difficult to realize the solubility of polyimide resin.
From described various quaternary carboxylic acids, select two or morely, under its acting in conjunction, can produce good result.Its total amount preferably accounts for 50～100mol% of quaternary carboxylic end group.
Except that the above-mentioned quaternary carboxylic acid of enumerating, content can be from Pyromellitic Acid, 1,2,4 less than the quaternary carboxylic acid of 50mol%, 5-hexanaphthene tetracarboxylic acid, 1,2,4, and 5-hexanaphthene tetracarboxylic acid, 2 is selected in two (3,4-dicarboxyl phenyl) HFC-236fa of 2-etc.
Select at least aly from described various diamines, its content need account for 50～100mol% of all diamines.If this molar percentage is less than 5mol%, then the thermal linear expansion coefficient of polyimide resin can be excessive, adopts casting method on tinsel during film forming again, and dried polyimide resin film can produce on tinsel and curl, influence processing characteristics afterwards.
More preferred content range is 10～80mol%.
Except that the above-mentioned diamine of enumerating, all the other diamines can be from polysiloxane diamine, N-(3-aminopropyl)-2-Pyrrolidone, N, N-two (3-aminopropyl) methylamine, isophorone diamine, 2,4-tolylene diamine, 2,6-tolylene diamine, 4,4-diaminodiphenyl oxide, 4 is selected in the 4-diaminodiphenyl-methane, 4,4-diamino-dicyclohexyl methane, p-diaminodiphenyl etc.
Polyimide resin of the present invention can make by the ordinary method of prior art.That is: described quaternary carboxylic acid and diamines are dissolved in the polar organic solvent, make it, generate polyamic acid,, obtain polyimide resin then with this polyamic acid imidization 0～80 ℃ of following hybrid reaction.
Described imidization method can be:
(1), in polyamic acid, add the azeotrope of small amount of toluene, dimethylbenzene and water, and be heated to 100～250 ℃, make it azeotropic, the physics dehydration that the water that generates in the imidization is removed from system.
(2), with acid anhydrides such as Glacial acetic acids, or cyanamide compounds such as dicyclohexyl carbimide makes polyamic acid generation dehydration reaction obtain the chemical dehydration method of polyimide as catalyzer.
The preferred method of making soluble polyimide resin disclosed in this invention is: add quaternary carboxylic acid and vulcabond and be heated to 200 ℃ in organic polar solvent, make it direct decarbonation and generate polyimide resin.When adopting this method, be preferably in aminated compoundss such as tin compound, triethylenediamine, methyl alcohol such as adding dibutyl tin laurate in the system and metal alcoholate such as receive as catalyzer.
Adopt intrinsic viscosity (in N-Methyl pyrrolidone, measuring down for 30 ℃) to characterize the molecular weight of polyimide resin disclosed in this invention, its optimum weight scope is 0.3～2.0dl/g.If the film toughness that obtains during film forming less than 0.3dl/g then in cast is not good, easily brittle failure.Molecular weight then can form insolubles during fabrication greater than 2.0dl/g, is difficult to preparation.
When making polyimide resin disclosed in this invention, earlier the dicarboxylic anhydride of quaternary carboxylic acid and the part of diamine or vulcabond are carried out polymerization, make oligopolymer, and then, can prepare segmented copolymer by this method with carrying out further polymerization in the dicarboxylic anhydride of remaining quaternary carboxylic acid and diamine or the vulcabond adding system.At this moment, preferably the dicarboxylic anhydride of quaternary carboxylic acid and the mol ratio between diamine or the vulcabond were controlled at 1: 1.Also can make one of reactant excessive, reach the purpose of control molecular chain end group by changing this mol ratio.Also can add and contain amine or cyanate ester monomer amino more than 3, obtain to have the polyimide resin of side chain.
Dissolve in the part organic solvent according to polyimide resin of the invention process, as: dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), gamma-butyrolactone, 1, the polar solvent of 3-dimethyl-non-proton property such as 2-imidazolone.Also dissolve in by in the above-mentioned arbitrarily solvent that two or more solvent is made into.
Also can will use as solvent after above-mentioned non-proton property polar solvent and the following solvent: alcoholic solvents such as glycol monomethyl methyl ether, diethylene glycol monomethyl ether, Virahol; Ether solvents such as ethylene glycol diethyl ether, diethylene glycol diethyl ether, tetrahydrofuran (THF); Ketones solvent such as 2-butanone, pimelinketone; Hydrocarbon polymer kind solvents such as dimethylbenzene.
Configuration contains the N-Methyl pyrrolidone solution of 15% (weight percent) polyimide resin, is applied on the slick surface such as polyester film, then with the solvent evaporates drying, makes the cast film that thickness is 30 μ m.The characteristic of described polyimide numerical value can show by the characteristic of this film.The tensile strength of this film is greater than 50N (30 μ m are thick, 20mm is wide), and thermal linear expansion coefficient is less than 4.0 * 10
-5℃
-1
Tensile strength reaction be the tensile strength of film, further says, reaction be film when being subjected to tensile stress, the complexity that its edge's generation is chapped, and film is chapped from the edge to the destructive resistivity of internal divergence for this.The size of tensile strength is relevant with the molecular weight of the composition of film and resin.The tensile strength of polyimide resin cast film must be greater than 50N (30 μ m be thick, 20mm is wide), and its performance just can reach and be used to prepare metal-foil composite and be further used in the requirement of making flexible electric circuit board.
When tensile strength during greater than 100N (30 μ m are thick, 20mm is wide) performance better.Greater than 200N (30 μ m are thick, 20mm is wide) is optimum.
The thermal linear expansion coefficient of polyimide resin of the present invention is less than 4.0 * 10
-5℃
-1If greater than this numerical value, then be difficult to keep the planeness on metal-foil composite surface, cause the processibility of flexible electric circuit board to descend, also promptly influence the dimensional stability of flexible electric circuit board.Thermal linear expansion coefficient is preferably 5.0 * 10
-6℃
-1～2.0 * 10
-5℃
-1
100 parts according to polyimide resin of the invention process in, add 10～100 parts thermosetting resin and be mixed and made into composition and use, improve the plasticity-and the Thermoadhesive of polyimide resin with this.Thermosetting resin makes its solvent resistance and thermotolerance obtain to promote by reacting with polyimide resin.
The preferred version of described thermosetting resin is as follows: phenolic resin, resol, Resins, epoxy, melmac etc.More preferred scheme is: modifying epoxy resin by organosilicon, phosphorous epoxy resin, polyphenyl ether modified Resins, epoxy, Racemic glycidol based epoxy resin etc.
The addition of thermosetting resin is 10～100 parts (with content of polyimide resin in the composition as 100 parts).If be less than 10 parts, then do not have desired effect; If surpass 100 parts, then the pliability after the film forming descends, and is not suitable for being used to make flexible electric circuit board.
In the composition of described polyimide resin, also can add other organic or inorganic additives as required and be used.As: the solidifying agent of silane coupling agent, titanium coupling agent, aluminum coupling agent, Phosphorus adhesion promotor, lubricant, thermosetting resin or weighting agents such as curing reaction catalyst, silicon-dioxide or aluminum oxide etc.
Use solvent mentioned above with described polyimide resin wiring solution-forming, be coated on then on synthetic resin film or the tinsel, after with solvent seasoning, make matrix material.The operation of coating can adopt common coating machine to finish, preferred comma type, back adhesive type, head formula coating machine.The drying conditions of coating machine is: 40～220 ℃ of following heat dryings 1～30 minute, and can adopt the FAR INFRARED HEATING drying simultaneously.Also can under protection of inert gas, adopt drying under reduced pressure down in 180～300 ℃.Dried thickness is 5～50 μ m, and preferred thickness is 10～30 μ m.
Below in conjunction with embodiment, the specific embodiment of the present invention is described.Before introducing embodiment, earlier the shared test method of all embodiment is described:
(1), preparation polyimide resin:
The dicarboxylic anhydride, 0.105mol vulcabond, the methoxyl group lithium 0.02g that in the reaction vessel of being furnished with stirrer, cooling for reflux pipe, thermometer, nitrogen access tube, add 0.01mol quaternary carboxylic acid.Add 90g again through molecular sieve carbon exsiccant N-Methyl pyrrolidone, feed nitrogen protection, stir down, reacted 5 hours at 110 ℃.
Append the 90gN-methyl-2-pyrrolidone, with temperature be increased to 180 ℃ and under this temperature stirring reaction 3 hours, obtain polyimide resin solution.
(2), casting film-forming:
Configuration contains the N-Methyl pyrrolidone solution of 15% (weight percent) polyimide resin, and coating thickness is on the polyester film of 100 μ m.
120 ℃ down logical warm air dryings divest the polyester film after 10 minutes, polyimide resin film is placed on the sheet glass, 200 ℃ of following drying under reduced pressure 12 hours.
Continuation was dry 3 hours of 280 ℃ of down logical nitrogen protections.
By adjusting the thickness of polyimide resin solution when being coated with, can make the film that thickness is 30 μ m.
This film under 20 ℃, is placed after 96 hours under the atmosphere of 65%RH, measured its tensile strength and thermal linear expansion coefficient.
(3), tensile strength:
According to the JISC2151-1990 of Japanese Industrial Standards (the electric plastics film test method of using), adopt the Type B sample, this sample is wide 20 millimeters, is that 20 ℃, humidity are to measure under the condition of 65%RH in temperature.
(4), thermal linear expansion coefficient:
To sample carry out dynamic mechanical test (be the thermo-mechanical analysis method, TMA), sample is wide 3 millimeters, thick 30 μ m, experiment condition is as follows: tension load 2g, 10 ℃/minute of heat-up rates, air atmosphere.
(5), the intrinsic viscosity of polyimide resin:
The 0.5g polyimide resin is dissolved in the N-Methyl pyrrolidone solution of 100ml, adopts dilution metering down at 30 ℃.
Embodiment 1:
Adopt above-mentioned experimental technique and following feedstock production polyimide resin:
3,3 ', 4, the dicarboxylic anhydride 32.2g of 4 '-tetracarboxylic acid benzophenone;
Toluene-2,4-diisocyanate, 4-vulcabond 14.4g;
4,4-diphenylmethanediisocyanate 2.6g;
3,3-dimethyl-4,4-benzidine 2.8g.
The intrinsic viscosity of this polyimide resin is 1.5dl/g.Its performance characterization sees Table 1.
Embodiment 2:
Adopt above-mentioned experimental technique and following feedstock production polyimide resin:
3,3 ', 4, the dicarboxylic anhydride 35.8g of 4 '-tetracarboxylic acid sulfobenzide
Toluene-2,4-diisocyanate, 4-vulcabond 9.0g;
4,4-dicyclohexyl methane diisocyanate 5.4g;
3,3 '-dimethyl-4,4 '-benzidine 8.3g.
The intrinsic viscosity of this polyimide resin is 1.2dl/g.Its performance characterization sees Table 1.
Embodiment 3:
Adopt above-mentioned experimental technique and following feedstock production polyimide resin:
3,3 ', 4, the dicarboxylic anhydride 35.8g of 4 '-tetracarboxylic acid sulfobenzide;
Toluene-2,4-diisocyanate, 4-vulcabond 10.8g;
4,4-dicyclohexyl methane diisocyanate 5.4g;
Naphthalene diisocyanate 4.4g.
The intrinsic viscosity of this polyimide resin is 1.1dl/g.Its performance characterization sees Table 1.
Embodiment 4:
The thickness that embodiment 1 prepared polyimide resin solution is coated in the production of paper tinsel powder company of FUKUDA METAL is on the rolled copper foil T5B surface of 35 μ m, uses warm air drying 10 minutes down at 120 ℃.It was 3 inches iron pipe surface that the Copper Foil that again this is coated with polyimide resin twists in diameter, and makes outside polyimide resin faces, and keeps this rolled state, 200 ℃ of following drying under reduced pressure 12 hours.Further temperature is increased to 280 ℃, drying is 3 hours under nitrogen atmosphere, makes the polyimide copper foil matrix material.Its performance characterization sees Table 2.
Comparative example 1:
Adopt above-mentioned experimental technique and following feedstock production polyimide resin:
3,3 ', 4, the dicarboxylic anhydride 32.2g of 4 '-tetracarboxylic acid benzophenone;
Toluene-2,4-diisocyanate, 4-vulcabond 9.0g;
Isophorone diisocyanate 10.9g;
The intrinsic viscosity of this polyimide resin is 0.9dl/g.Its performance characterization sees Table 1.
Table 1:
| Resin | Tensile strength (N/20mm) | Thermal linear expansion coefficient (℃ -1)? |
| Embodiment 1 | 230? | 2.9×10 -5 |
| Embodiment 2 | 170? | 2.2×10 -5 |
| Embodiment 3 | 150? | 2.7×10 -5 |
| Comparative example 1 | 110? | 6.0×10 -5 |
Table 2:
| Project | Measured value | Condition determination |
| Stripping strength with Copper Foil | 0.9N/cm? | 5cm/min、180℃? |
| Folding strength (MIT) | 350 times | MIT folding strength trier, sample are wide 15 millimeters, loading 5N, R0.8 millimeter |
| Straight weldering property | 300℃×20s? | Copper Foil is placed downwards in the soldering pot, observes expansion and peels off phenomenon |
| Wire insulation resistance | 2.5×10 12Ω | Be etched into the wide 1mm of conductor, long 50mm stripe shape sample determination |
All samples are that 20 ℃, the indoor of 65%RH are measured after 96 hours placement again in envrionment conditions all.
As mentioned above, we are illustrated according to aim of the present invention fully, but the present invention is not limited to the foregoing description and implementation method.The practitioner of correlative technology field can carry out different variations and enforcement in the scope of technological thought permission of the present invention.
Claims (6)
1. soluble polyimide resin, comprise quaternary carboxylic end group and diamine end group, it is characterized in that: after this soluble polyimide resin cast film forming, its thickness is 30 μ m, tensile strength when width is 20mm is greater than 50N, and thermal linear expansion coefficient is less than 4.0 * 10
-5℃
-1
The described quaternary carboxylic end group of 100mol% is an at least a end group in the following quaternary carboxylic acid: 3,3 ', 4, and 4 '-diphenyl sulfone tetraformic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic;
The described diamine end group of 100mol% is an end group at least a in the following diamine: Ursol D, 1,5-naphthylene diamine, 2,6-naphthylene diamine.
2. composition that comprises soluble polyimide resin as claimed in claim 1, it is characterized in that: said composition comprises 100 parts of soluble polyimide resins, 10～100 parts of thermosetting resins;
Described soluble polyimide resin comprises quaternary carboxylic end group and diamine end group, and after the described soluble polyimide resin cast film forming, its thickness is 30 μ m, and the tensile strength when width is 20mm is greater than 50N, and thermal linear expansion coefficient is less than 4.0 * 10
-5℃
-1
The described quaternary carboxylic end group of 100mol% is an at least a end group in the following quaternary carboxylic acid: 3,3 ', 4, and 4 '-diphenyl sulfone tetraformic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic;
The described diamine end group of 100mol% is an end group at least a in the following diamine: Ursol D, 1,5-naphthylene diamine, 2,6-naphthylene diamine.
3. matrix material that uses soluble polyimide resin as claimed in claim 1 is characterized in that: this matrix material comprises tinsel and is coated in soluble polyimide resin on this metal foil surface,
Described soluble polyimide resin comprises quaternary carboxylic end group and diamine end group, and after the described soluble polyimide resin cast film forming, its thickness is 30 μ m, and the tensile strength when width is 20mm is greater than 50N, and thermal linear expansion coefficient is less than 4.0 * 10
-5℃
-1
The described quaternary carboxylic end group of 100mol% is an at least a end group in the following quaternary carboxylic acid: 3,3 ', 4, and 4 '-diphenyl sulfone tetraformic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic;
The described diamine end group of 100mol% is an end group at least a in the following diamine: Ursol D, 1,5-naphthylene diamine, 2,6-naphthylene diamine.
4. matrix material that uses composition as claimed in claim 2 is characterized in that: this matrix material comprises tinsel and is coated in the composition of the soluble polyimide resin on this metal foil surface;
Described composition comprises 100 parts of soluble polyimide resins, 10～100 parts of thermosetting resins;
Described soluble polyimide resin comprises quaternary carboxylic end group and diamine end group, and after the described soluble polyimide resin cast film forming, its thickness is 30 μ m, and the tensile strength when width is 20mm is greater than 50N, and thermal linear expansion coefficient is less than 4.0 * 10
-5℃
-1
The described quaternary carboxylic end group of 100mol% is an at least a end group in the following quaternary carboxylic acid: 3,3 ', 4, and 4 '-diphenyl sulfone tetraformic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic;
The described diamine end group of 100mol% is an end group at least a in the following diamine: Ursol D, 1,5-naphthylene diamine, 2,6-naphthylene diamine.
5. flexible electric circuit board that uses matrix material as claimed in claim 3, it is characterized in that: at least a portion of this flexible electric circuit board is the matrix material of soluble polyimide resin, and this matrix material comprises tinsel and the soluble polyimide resin that is coated on this metal foil surface;
Described soluble polyimide resin comprises quaternary carboxylic end group and diamine end group, and after the described soluble polyimide resin cast film forming, its thickness is 30 μ m, and the tensile strength when width is 20mm is greater than 50N, and thermal linear expansion coefficient is less than 4.0 * 10
-5℃
-1
The described quaternary carboxylic end group of 100mol% is an at least a end group in the following quaternary carboxylic acid: 3,3 ', 4, and 4 '-diphenyl sulfone tetraformic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic;
The described diamine end group of 100mol% is an end group at least a in the following diamine: Ursol D, 1,5-naphthylene diamine, 2,6-naphthylene diamine.
6. flexible electric circuit board that uses matrix material as claimed in claim 4, it is characterized in that: at least a portion of this flexible electric circuit board is the matrix material of the composition of soluble polyimide resin, this matrix material comprises tinsel and is coated in the composition of the soluble polyimide resin on this metal foil surface that described composition comprises 100 parts of soluble polyimide resins, 10～100 parts of thermosetting resins;
Described soluble polyimide resin comprises quaternary carboxylic end group and diamine end group, and after the described soluble polyimide resin cast film forming, its thickness is 30 μ m, and the tensile strength when width is 20mm is greater than 50N, and thermal linear expansion coefficient is less than 4.0 * 10
-5℃
-1
The described quaternary carboxylic end group of 100mol% is an at least a end group in the following quaternary carboxylic acid: 3,3 ', 4, and 4 '-diphenyl sulfone tetraformic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic;
The described diamine end group of 100mol% is an end group at least a in the following diamine: Ursol D, 1,5-naphthylene diamine, 2,6-naphthylene diamine.
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| CN2007101918171A CN101260188B (en) | 2007-12-14 | 2007-12-14 | Soluble polyimide resin and composition thereof, composite material and flexible circuit board using the resin or composition thereof |
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| CN2007101918171A CN101260188B (en) | 2007-12-14 | 2007-12-14 | Soluble polyimide resin and composition thereof, composite material and flexible circuit board using the resin or composition thereof |
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| CN101787129A (en) * | 2010-03-04 | 2010-07-28 | 南京航空航天大学 | Soluble and high-temperature resistant aromatic polyimide and preparation method thereof |
| CN102391532B (en) * | 2011-08-26 | 2012-11-14 | 朱宏清 | Biaxially oriented polyimide film for flexible printed circuit board base material and preparation method of biaxially oriented polyimide film |
| CN103785602B (en) * | 2014-01-27 | 2016-08-31 | 中原工学院 | Electrostatic coating composite solution prepares the method for jumbo double-faced flexible aluminium foil |
| CN109817852A (en) * | 2018-12-29 | 2019-05-28 | 武汉依麦德新材料科技有限责任公司 | A kind of lithium ion battery outer cover material and preparation method thereof |
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| CN1872896A (en) * | 2005-06-03 | 2006-12-06 | 长春人造树脂厂股份有限公司 | New type polyimide resin, and preparation method |
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