CN105015099B - Polyimides/metal composite laminated plates and preparation method thereof - Google Patents
Polyimides/metal composite laminated plates and preparation method thereof Download PDFInfo
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- CN105015099B CN105015099B CN201410178745.7A CN201410178745A CN105015099B CN 105015099 B CN105015099 B CN 105015099B CN 201410178745 A CN201410178745 A CN 201410178745A CN 105015099 B CN105015099 B CN 105015099B
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Abstract
The present invention relates to polyimides/metal composite laminated plates and preparation method thereof, wherein polyimides/metal composite laminated plates sequentially recline overlap comprising the first Copper Foil, the first thermoplastic polyimide film, the first Thermocurable polyimide film and the second thermoplastic polyimide film that are posted by the one side of first Copper Foil, and the first thermoplastic polyimide film, the first Thermocurable polyimide film and the second thermoplastic polyimide film.Due to saving the use of glue-line, polyimides of the invention/metal composite laminated plates can be used to be thinned flexible printed wiring board and with good soldering resistance, dimensional stability and peel strength；Meanwhile, by with being not less than 170g μm/m2First Thermocurable polyimide film of the aqueous vapor penetrance of day and the second thermoplastic polyimide film, the polyimides/metal composite laminated plates can avoid delamination and the generation of albinism.
Description
Technical field
On a kind of polyimides/metal composite laminated plates and preparation method thereof, espespecially one kind can save glue-line to the present invention
Polyimides/metal composite laminated plates and preparation method thereof.
Background technology
Aromatic polyimides is because with high-temperature resistant, anti-chemical, excellent machinery and the characteristic such as electrically, widely being made
The flexible printer circuit of the electronic components in the electronic product of notebook computer, consumer electronics and communication hand-held
Plate (flexible printed circuit board, FPCB).
The manufacture of existing flexible printed wiring board, with polyimide film as base material, in the both sides of polyimide film
Face is respectively coated epoxy resin or acryl resin to shape glue-line, then two metal copper foils is fitted in through two glue-lines respectively poly-
On the two sides of acid imide film, the flexible printed wiring board is obtained.
However, the glue-line being made up of epoxy resin or acryl resin can for heat-resisting, the resistance to combustion of flexible printed wiring board,
Anti-ization exerts an adverse impact with dimensional stability, and glue-line has suitable thickness, it is impossible to meet flexible printed wiring board
Thinning tendency.
The content of the invention
In view of the shortcoming of above-mentioned prior art, the polyimides for saving glue-line it is an object of the invention to provide a kind of/
Metal composite laminated plates and preparation method thereof.
In order to can reach foregoing goal of the invention, the technological means that the present invention is taken is multiple for a kind of polyimides/metal
Laminated plates are closed, wherein including：
First metal film；
First thermoplastic polyimide film, it reclines and is overlapped on the one side of first metal film；
First Thermocurable polyimide film, it reclines and is overlapped in first thermoplastic polyimide film away from described first
On the one side of metal film, and the first Thermocurable polyimide film aqueous vapor penetrance be not less than 170 grams-micron/square
(g- μm/m of rice-day2-day)；And,
Second thermoplastic polyimide film, it reclines and is overlapped in the first Thermocurable polyimide film away from described first
On the one side of thermoplastic polyimide film, and the aqueous vapor penetrance of second thermoplastic polyimide film is not less than described
The aqueous vapor penetrance of one Thermocurable polyimide film.
The polyimides/metal composite laminated plates are due to that without glue-line, can meet the slim of flexible printed wiring board
The trend of change and with good soldering resistance, dimensional stability and peel strength；Meanwhile, by be not less than 170g- μm/
m2First Thermocurable polyimide film of the aqueous vapor penetrance of-day and the second thermoplastic polyimide film, the polyimides/
Metal composite laminated plates can avoid delamination and the generation of albinism.
In one embodiment, described polyimides/metal composite laminated plates are overlapped in second heat comprising reclining
Plastic polyimide film is away from the second metal film on the one side of the first Thermocurable polyimide film.
In another embodiment, described polyimides/metal composite laminated plates include the 3rd TPI
Film, the 3rd thermoplastic polyimide film be stacked and placed on second metal film and second thermoplastic polyimide film it
Between.
In yet another embodiment, described polyimides/metal composite laminated plates include the second Thermocurable polyimide
Film, the second Thermocurable polyimide film is stacked and placed on the 3rd thermoplastic polyimide film and the second thermoplasticity polyamides
Between imines film.
In still another embodiment, described polyimides/metal composite laminated plates include the 4th TPI
Film, the 4th thermoplastic polyimide film is stacked and placed on the second Thermocurable polyimide film with the second thermoplasticity polyamides
Between imines film.
Preferably, the aqueous vapor penetrance of second thermoplastic polyimide film is not less than 200g- μm/m2-day。
Preferably, the aqueous vapor penetrance of the first Thermocurable polyimide film is not less than 200g- μm/m2-day。
Preferably, first thermoplastic polyimide film, the first Thermocurable polyimide film and described second
The gross thickness of thermoplastic polyimide film is between 9 microns (μm) between 25 microns (μm).
Preferably, first thermoplastic polyimide film, the first Thermocurable polyimide film and described second
The overall aqueous vapor penetrance of thermoplastic polyimide film is not less than 180g- μm/m2-day。
In order to can reach foregoing goal of the invention, the technological means that the present invention is taken is multiple for a kind of polyimides/metal
The preparation method of laminated plates is closed, its step is included：
First diamine monomer, the first reactive monomer and the first dianhydride monomer are polymerized in the first solvent, to obtain
Thermocurable polyimide predecessor, first reactive monomer is selected from the group of following composition：2,2'- is double (4- aminophenyls)
Double (3- amino-benzene oxygens) benzene (1,3-bis (3- of propane (2,2'-bis (4-aminophenyl) propane), 1,3-
Aminophenoxy) benzene), 4,4'- (1,3- phenylenes diisopropylidene) diphenylamines (4,4'- (1,3-
Phenylenediisopropylidene) bisaniline, Bisaniline-M), double (4- aminophenyls) fluorenes of 9,9'- (9,
9'-bis (4-aminophenyl) fluorene), polypropyleneoxide diamine (polyoxypropylenediamine), and with described
On the basis of the total mole number of diamine monomer and the reactive monomer, the molal quantity of first reactive monomer between 3.00 to
Between 7.00 molar percentages；
Second diamine monomer, the second reactive monomer and the second dianhydride monomer are polymerized in the second solvent, to obtain
TPI predecessor, second reactive monomer is selected from the group of following composition：2,2'- is double (4- aminophenyls)
Double (3- amino-benzene oxygens) benzene of propane, 1,3-, 4,4'- (1,3- phenylenes diisopropylidene) diphenylamines, double (the 4- amino of 9,9'-
Phenyl) fluorenes and polypropyleneoxide diamine, and with the total mole number of second diamine monomer and second reactive monomer as base
Standard, the molal quantity of second reactive monomer is between 35.00 to 65.00 molar percentages；
The TPI predecessor is coated with the one side of the first Copper Foil, to form the first thermoplasticity polyamides
Imines precursor layer；
The Thermocurable polyimide predecessor is coated with the first TPI precursor layer away from described
On the one side of the first Copper Foil, to be molded the first Thermocurable polyimide precursor layer；
The TPI predecessor is coated with the first Thermocurable polyimide precursor layer away from described
On the one side of the first TPI precursor layer, to be molded the second TPI precursor layer；And,
By the first TPI precursor layer, the first Thermocurable polyimide precursor layer and described
The cyclisation of second TPI precursor layer is the first thermoplastic polyimide film, the first Thermocurable polyimide film and the
Two thermoplastic polyimide films, obtain the polyimides/metal composite laminated plates.
Described preparation method, can be obtained the polyimides/metal composite laminated plates without glue-line, and due to not having
Glue-line, the polyimides/metal composite laminated plates can have the low and good soldering resistance of thickness, dimensional stability and peel off strong
Degree；Additionally, by the use of first reactive monomer and second reactive monomer, obtained by described preparation method
Polyimides/metal composite laminated plates, its first Thermocurable polyimide film and the second thermoplastic polyimide film have big
In or equal to 170g- μm/m2The aqueous vapor penetrance of-day, then be avoided that delamination and the generation of albinism.
Preferably, by the first TPI precursor layer, the first Thermocurable polyimide forerunner
Nitride layer and the second TPI precursor layer cyclisation are first thermoplastic polyimide film, first heat
Solidity polyimide film and second thermoplastic polyimide film, obtain the step of the polyimides/metal composite laminated plates
Suddenly include：
By the first TPI precursor layer, the first Thermocurable polyimide precursor layer and described
The cyclisation of second TPI precursor layer is first thermoplastic polyimide film, the first thermosetting polyamides is sub-
The step of amine film and second thermoplastic polyimide film；And,
The second Copper Foil is pressed in second thermoplastic polyimide film away from the first Thermocurable polyimide film
On one side, the step of obtain the polyimides/metal composite laminated plates.
Preferably, by the first TPI precursor layer, the first Thermocurable polyimide forerunner
Nitride layer and the second TPI precursor layer cyclisation are first thermoplastic polyimide film, first heat
Solidity polyimide film and second thermoplastic polyimide film, obtain the step of the polyimides/metal composite laminated plates
Suddenly include：
At 80 DEG C to 150 DEG C except under solvent temperature, the first TPI precursor layer, described the are removed
Solvent contained by one Thermocurable polyimide precursor layer and the second TPI precursor layer, obtains through going
Except the first TPI precursor layer of solvent, the first Thermocurable polyimide precursor layer through removing solvent and warp
The step of removing the second TPI precursor layer of solvent；And
By the first TPI precursor layer, first thermosetting through removing solvent through removing solvent
Property polyimides precursor layer and it is described through remove solvent the second TPI precursor layer simultaneously be sequentially heated to
160 DEG C to 190 DEG C of temperature, 190 DEG C to 300 DEG C of temperature and 300 DEG C to 350 DEG C of temperature are described first to be cyclized respectively
Thermoplastic polyimide film, the first Thermocurable polyimide film and second TPI, obtain described poly-
The step of acid imide/metal composite laminated plates.
Preferably, first diamine monomer and second diamine monomer can for 3,4'- diamino-diphenyls ether (3,
4'-diaminodiphenyl ether), it is 4,4'- diamino-diphenyls ether (4,4'-diaminodiphenyl ether), right
Phenylenediamine (p-phenylenediamine), m-phenylene diamine (MPD) (m-phenylenediamine), 3,5- diaminobenzoic acids (3,5-
Diaminobenzoic acid), double (4- aminophenyls) propane (2,2'-bis (4-aminophenyl) propane) of 2,2'-,
4,4'- diaminodiphenyl-methanes (4,4'-diaminodiphenyl methane), 4,4'- diamino diphenyl sulfones (4,4'-
Diaminodiphenyl sulfone), 3,3'- diamino diphenyl sulfones (3,4'-diaminodiphenyl sulfone), 4,
Double (4- amino-benzene oxygens) benzene (1,3- of 4'- diamino diphenyl sulfides (4,4'-diaminodiphenyl sulfide), 1,3-
Bis (4-aminophenoxy) benzene), double (3- amino-benzene oxygens) benzene (1,3-bis (3-aminophenoxy) of 1,3-
Benzene), double (4- amino-benzene oxygens) benzene (1,4-bis (4-aminophenoxy) benzene) of 1,4-, double (the 4- amino of 4,4-
Phenoxy group)-biphenyl (4,4-bis (3-aminophenoxy) biphenyl), double [4- (4- amino-benzene oxygens) phenyl] third of 2,2'-
Double [4- (3- amino-benzene oxygens) phenyl] third of alkane (2,2'-bis [4- (4-aminophenoxy) phenyl] propane), 2,2'-
Alkane (2,2'-bis [4- (3-aminophenoxy) pheny] propane), 2,2'- dimethyl -4,4'- benzidines (2,
2'-dimethyl-4,4'-diaminobiphenyl), 3,3'- dimethyl -4,4'- benzidines (3,3'-dimethyl-
4,4'-diaminobiphenyl), double (4- aminophenyls) fluorenes (9,9'-bis (4-aminophenyl) fluorene) of 9,9'-,
2,6- diamino-pyridines (2,6-diaminopyridine), polypropyleneoxide diamine (polyoxypropylenediamine), 4,
4'- (1,3- phenylenes diisopropylidene) diphenylamines (4,4'- (1,3-phenylenediisopropylidene)
Bisaniline, Bisaniline-M), 4,4'- (Isosorbide-5-Nitrae-phenylene diisopropylidene) diphenylamines (4,4'- (Isosorbide-5-Nitrae-
Phenylenediisopropylidene) bisaniline, Bisaniline-P), norbornane dimethylamine (norbornane
Dimethylamine, NBDA) and combinations thereof, but be not limited.
It is further preferred that group of the polypropyleneoxide diamine purchased from following composition： D230、D400 and D2000。
Preferably, first dianhydride monomer and second dianhydride monomer can be equal benzene tertacarbonic acid's dianhydride
(pyromellitic dianhydride), 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides (3,3', 4,4'-biphenyl
Tetracarboxylic dianhydride), 3,3',4,4' benzophenone tetracarboxylic dianhydride (3,3', 4,4'-
Benzophenone tetracarboxylic dianhydride), the phthalic acid dianhydride (4,4'- of 4,4'- oxygen two
Oxydiphthalic dianhydride), 3,3', 4,4'- diphenyl sulfone tetracarboxylic dianhydrides (3,3', 4,4'-
Diphenylsulfone tetracarboxylic dianhydride), ethylene glycol-bis- trimellitic anhydride (ethylene
Glycol-bis-trimellitate anhydride), 1,2,3,4- butane tetracarboxylic acid dianhydrides (1,2,3,4-
Butanetetracarboxylic dianhydride), 1,2,3,4- pentamethylene tetracarboxylic dianhydrides (1,2,3,4-
Cyclopentanetetracarboxylic dianhydride) and combinations thereof, but be not limited.
Preferably, first solvent and second solvent can for tetrahydrofuran (tetrahydrofuran, THF),
DMF (N, N-dimethylformide, DMF), DMA (N, N-
Dimethylacetamide, DMAC), METHYLPYRROLIDONE (N-methyl-2-pyrrolidone, NMP), γ-Ding Nei
Ester (γ-butyrolactone, GBL) and combinations thereof, but be not limited.
Preferably, it is described on the basis of the total mole number of first diamine monomer and first reactive monomer
The molal quantity of the first reactive monomer is between 3.00 to 7.00 molar percentages.
Preferably, it is described on the basis of the total mole number of second diamine monomer and second reactive monomer
The molal quantity of the second reactive monomer is between 35.00 to 65.00 molar percentages.
Brief description of the drawings
Fig. 1 is the side elevational cross-section of the polyimides/metal composite laminated plates of embodiments of the invention 1 to 9 and comparative example 1
Figure.
Fig. 2 is the side cutaway view of the polyimides/metal composite laminated plates of embodiments of the invention 10.
Fig. 3 is the side cutaway view of the polyimides/metal composite laminated plates of embodiments of the invention 11.
Fig. 4 is the side cutaway view of the polyimides/metal composite laminated plates of embodiments of the invention 12.
Fig. 5 is the side cutaway view of the polyimides/metal composite laminated plates of embodiments of the invention 13.
Fig. 6 is the side cutaway view of the polyimides/metal composite laminated plates of comparative example 2 to 7 of the invention.
Fig. 7 is the side cutaway view of the polyimides/metal composite laminated plates of comparative example 8 to 13 of the invention.
Symbol description
10 first Copper Foils
20 first thermoplastic polyimide films
30 first Thermocurable polyimide films
40 second thermoplastic polyimide films
50 second Copper Foils
60 the 3rd thermoplastic polyimide films
70 second Thermocurable polyimide films
80 the 4th thermoplastic polyimide films
10A, 10B, 10C Copper Foil
20B, 40C thermoplastic polyimide film
30B, 30C Thermocurable polyimide film.
Specific embodiment
The preparation of the Thermocurable polyimide predecessor of preparation example 1
In 1000 milliliters of four mouthfuls of reactors of nitrogen are passed through, by 19.877 grams of p-phenylenediamine and the 4 of 1.940 grams,
During 4'- diamino-diphenyls ether is dissolved in 425 grams of METHYLPYRROLIDONE at a temperature of 25 ± 5 DEG C, diamines list is obtained
Liquid solution；Add the diamine monomer solution to carry out first polymerisation 8.029 grams of equal benzene tertacarbonic acid's dianhydride again, treat first
After polymerisation is abundant, the solution through first polymerization is obtained；Afterwards, by the 3,3' of 45.60 grams, 4,4'- diphenyl tetrabasic carboxylic acids two
Acid anhydride in three batches it is secondary add warp for the first time polymerization solution in and continue stirring 4 hours to carry out after polymerization reaction, it is secondary gather
After conjunction reaction terminates, the Thermocurable polyimide acid predecessor of this preparation example is obtained.The Thermocurable polyimide acid of this preparation example
Predecessor is denoted as PI-1.
The preparation of the Thermocurable polyimide predecessor of preparation example 2
This preparation example is roughly the same with preparation example 1, and this preparation example is as described below with the difference of preparation example 1.
This preparation example is by 19.159 grams of p-phenylenediamine, 1.870 grams of 4,4'- diamino-diphenyls ether and the first reaction
Property monomer dissolve 425 grams of METHYLPYRROLIDONE, obtain the diamine monomer solution, and by 7.739 grams of equal benzene tetracarboxylic acid
Acid dianhydride is added to the diamine monomer solution to carry out first polymerisation and obtain the solution of warp polymerization for the first time.
Wherein, first reactive monomer of this preparation example be polyoxypropylene diamine monomer (D400), its
Usage amount is 2.260 grams, and with the total mole number of p-phenylenediamine, 4,4'- diamino-diphenyls ether and first reactive monomer
On the basis of, the content of first reactive monomer is 2.74 molar percentages.
Additionally, the Thermocurable polyimide acid predecessor of this preparation example, is denoted as PI-2.
The preparation of the Thermocurable polyimide predecessor of preparation example 3
This preparation example is roughly the same with preparation example 1, and this preparation example is as described below with the difference of preparation example 1.
This preparation example is by 18.708 grams of p-phenylenediamine, 1.826 grams of 4,4'- diamino-diphenyls ether and the first reaction
Property monomer is dissolved in 425 grams of METHYLPYRROLIDONE, obtains the diamine monomer solution；Again by 7.557 grams of equal benzene four
Carboxylic acid dianhydride is added to the diamine monomer solution, to carry out first polymerisation and obtain the solution of warp polymerization for the first time.
Wherein, first reactive monomer of this preparation example be polyoxypropylene diamine monomer (D400), its
Usage amount is 3.772 grams, and with the total mole number of p-phenylenediamine, 4,4'- diamino-diphenyls ether and first reactive monomer
On the basis of, the content of first reactive monomer is 4.59 molar percentages.
Additionally, the Thermocurable polyimide acid predecessor of this preparation example is denoted as PI-3.
The preparation of the Thermocurable polyimide predecessor of preparation example 4
This preparation example is roughly the same with preparation example 1, and this preparation example is as described below with the difference of preparation example 1.
This preparation example is by 19.044 grams of p-phenylenediamine, 1.858 grams of 4,4'- diamino-diphenyls ether and the first reaction
Property monomer is dissolved in 425 grams of METHYLPYRROLIDONE, obtains the diamine monomer solution；Again by 7.692 grams of equal benzene four
Carboxylic acid dianhydride is added into the diamine monomer solution, to carry out first polymerisation and obtain the solution of warp polymerization for the first time.
Wherein, first reactive monomer of this preparation example is double (4- aminophenyls) fluorenes of 9,9-, and its usage amount is 2.263
Gram, and with the total mole number of p-phenylenediamine, 4,4'- diamino-diphenyls ether and first reactive monomer on the basis of, this first
The content of reactive monomer is 3.39 molar percentages.
Additionally, the Thermocurable polyimide acid predecessor of this preparation example is denoted as PI-4.
The preparation of the Thermocurable polyimide predecessor of preparation example 5
This preparation example is roughly the same with preparation example 1, and this preparation example is as described below with the difference of preparation example 1.
This preparation example is by 18.490 grams of p-phenylenediamine, 1.804 grams of 4,4'- diamino-diphenyls ether and the first reaction
Property monomer is dissolved in 425 grams of METHYLPYRROLIDONE, obtains the diamine monomer solution；Again by 7.469 grams of equal benzene four
Carboxylic acid dianhydride is added into the diamine monomer solution, to carry out first polymerisation and obtain the solution of warp polymerization for the first time.
Wherein, first reactive monomer of this preparation example is double (4- aminophenyls) fluorenes of 9,9-, and its usage amount is 3.772
Gram, and with the total mole number of p-phenylenediamine, 4,4'- diamino-diphenyls ether and first reactive monomer on the basis of, this first
The content of reactive monomer is 5.67 molar percentages.
Additionally, the Thermocurable polyimide acid predecessor of this preparation example is denoted as PI-5.
The preparation of the Thermocurable polyimide predecessor of preparation example 6
This preparation example is roughly the same with preparation example 1, and this preparation example is as described below with the difference of preparation example 1.
This preparation example is that 19.322 grams of p-phenylenediamine and the first reactive monomer are dissolved in 425 grams of N- methyl -2-
In pyrrolidones, the diamine monomer solution is obtained；7.512 grams of equal benzene tertacarbonic acid's dianhydride is added to the diamine monomer solution again
In, to carry out first polymerisation and obtain the solution of warp polymerization for the first time.
Wherein, first reactive monomer of this preparation example comprising polypropyleneoxide diamine monomer (D400) and
9,9- double (4- aminophenyls) fluorenes, the usage amount of polypropyleneoxide diamine monomer is 2.057 grams, 9,9- double (4- aminophenyls) fluorenes
Usage amount is 2.667 grams, and on the basis of the total mole number of p-phenylenediamine and first reactive monomer, first reactivity is single
The content of body is 6.50 molar percentages.
Additionally, the Thermocurable polyimide predecessor of this preparation example is denoted as PI-6.
The preparation of the TPI predecessor of preparation example 7
It is in 1000 milliliters of four mouthfuls of reactors of nitrogen are passed through, 5.515 grams of p-phenylenediamine and the second reactivity is single
During body is dissolved in 425 grams of METHYLPYRROLIDONE at a temperature of 25 ± 5 DEG C, diamine monomer solution is obtained；Again will
45.60 grams of 3,3', 4,4'- biphenyltetracaboxylic dianhydride are in three batches in secondary addition diamine monomer solution and to continue stirring 4 small
When to carry out polymerisation, after polymerisation terminates, obtain the TPI predecessor of this preparation example.This preparation example
TPI predecessor be denoted as TPI-1.
Wherein, second reactive monomer of this preparation example is double (3- amino-benzene oxygens) benzene of 1,3-, and its usage amount is
27.693 grams, and on the basis of the total mole number of p-phenylenediamine and second reactive monomer, second reactive monomer contains
It is 65.00 molar percentages to measure.
The preparation of the TPI predecessor of preparation example 8
This preparation example is roughly the same with preparation example 7, and this preparation example is as described below with the difference of preparation example 7.
This preparation example is that 5.516 grams of p-phenylenediamine and second reactive monomer are dissolved at a temperature of 25 ± 5 DEG C
In 425 grams of METHYLPYRROLIDONE, the diamine monomer solution is obtained.
Wherein, second reactive monomer of this preparation example comprising 4,4'- (1,3- phenylene diisopropylidene) diphenylamines and
2,2'- double (4- aminophenyls) propane, the usage amount of 4,4'- (1,3- phenylene diisopropylidene) diphenylamines is 23.435 grams,
The usage amounts of 2,2'- double (4- aminophenyls) propane are 5.990 grams, and always rubbing with p-phenylenediamine and second reactive monomer
On the basis of your number, the content of second reactive monomer is 61.80 molar percentages.
The TPI predecessor of this preparation example is denoted as TPI-2.
The preparation of the TPI predecessor of preparation example 9
This preparation example is roughly the same with preparation example 7, and this preparation example is as described below with the difference of preparation example 7.
This preparation example is 25 ± 5 by double (4- amino-benzene oxygens) benzene of 23.821 grams of 1,3- and second reactive monomer
It is dissolved at a temperature of DEG C in 425 grams of METHYLPYRROLIDONE, obtains the diamine monomer solution, then by 14.383 grams
Equal benzene tertacarbonic acid's dianhydride adds the diamine monomer solution to carry out first polymerisation, after first polymerisation is abundant, obtains
Through the solution of first polymerization；Afterwards, two batches are divided to add the warp just the 3,3' of 20.00 grams, 4,4'- biphenyltetracaboxylic dianhydrides
In the solution of secondary polymerization and continue stirring 4 hours to carry out after polymerization reaction, after polymerization reaction terminate after, obtain this system
The TPI acid predecessor of standby example.
Wherein, second reactive monomer of this preparation example is 4,4'- (1,3- phenylene diisopropylidene) diphenylamines, and it makes
Consumption is 18.735 grams, and with the total mole number of double (4- amino-benzene oxygens) benzene of 1,3- and second reactive monomer on the basis of,
The content of second reactive monomer is 35.87 molar percentages.
Additionally, the TPI predecessor of this preparation example is denoted as TPI-3.
The preparation of the TPI predecessor of preparation example 10
This preparation example is roughly the same with preparation example 7, and this preparation example is as described below with the difference of preparation example 7.
This preparation example is 25 ± 5 by double (4- amino-benzene oxygens) benzene of 18.196 grams of 1,3- and second reactive monomer
It is dissolved at a temperature of DEG C in 425 grams of METHYLPYRROLIDONE, obtains the diamine monomer solution, then by 10.466 grams
Equal benzene tertacarbonic acid's dianhydride adds the diamine monomer solution to carry out first polymerisation, after first polymerisation is abundant, obtains
Through the solution of first polymerization；Afterwards, two batches are divided to add the warp just the 3,3' of 22.00 grams, 4,4'- biphenyltetracaboxylic dianhydrides
In the solution of secondary polymerization and continue stirring 4 hours to carry out after polymerization reaction, after polymerization reaction terminate after, obtain this system
The TPI acid predecessor of standby example.
Wherein, second reactive monomer of this preparation example is 2', double (4- aminophenyls) propane of 2-, and its usage amount is
25.581 grams, and with the total mole number of double (4- amino-benzene oxygens) benzene of 1,3- and second reactive monomer on the basis of, this second
The content of reactive monomer is 50.00 molar percentages.
Additionally, the TPI predecessor of this preparation example is denoted as TPI-4.
1 polyimides of embodiment/metal composite laminated plates and preparation method thereof
As shown in figure 1, the polyimides of the present embodiment/metal composite laminated plates include the first Copper Foil 10, the first thermoplasticity
Polyimide film 20, the first Thermocurable polyimide film 30, the second thermoplastic polyimide film 40 and the second Copper Foil 50.This first
Thermoplastic polyimide film 20, the first Thermocurable polyimide film 30 and second thermoplastic polyimide film 40 sequentially recline
It is overlapped between first Copper Foil 10 and second Copper Foil 50, first thermoplastic polyimide film 20 and the phase of the first Copper Foil 10
Connect, second thermoplastic polyimide film 40 connects with second Copper Foil 50.Wherein, first thermoplastic polyimide film 20 and
The thickness of second thermoplastic polyimide film 40 is 2 microns, and the thickness of the first Thermocurable polyimide film 30 is 15 microns.
As shown in figure 1, the polyimides of the present embodiment/metal composite laminated plates preparation method is as described below.
First TPI-1 is coated on the one side of first Copper Foil 10, form the first TPI precursor layer；
PI-5 is coated on one side of the first TPI precursor layer away from first Copper Foil 10 again, forms first
Thermocurable polyimide precursor layer；Again by TPI-1 coat the first Thermocurable polyimide precursor layer away from this first
On the one side of TPI precursor layer, the second TPI precursor layer is formed.
Then, with 80 DEG C to 150 DEG C except solvent temperature remove the first TPI precursor layer, this first
Contained solvent, i.e. N- methyl in Thermocurable polyimide precursor layer and the second TPI precursor layer-
2-Pyrrolidone.
Afterwards, in the environment of containing nitrogen, by the first TPI precursor layer through removing solvent, through removal
First Thermocurable polyimide precursor layer of solvent and the second TPI precursor layer three through removing solvent
160 DEG C to 190 DEG C of temperature, 190 DEG C to 300 DEG C of temperature and 300 DEG C to 350 DEG C of temperature are sequentially heated to simultaneously to carry out
Cyclization；After the cyclization terminates, this is through removing the first TPI precursor layer cyclisation of solvent to be somebody's turn to do
First thermoplastic polyimide film 20, this is first heat through removing the first Thermocurable polyimide precursor layer cyclisation of solvent
Solidity polyimide film 30, the second TPI precursor layer cyclisation through removing solvent is second thermoplastic poly
Acid imide film 40.
Finally, by second Copper Foil 50 at 320 DEG C to 380 DEG C pressing-in temp, 50 to double centner power/square centimeter
(KgF/cm2)Pressing pressure under be pressed on second thermoplastic polyimide film 40 away from the first Thermocurable polyimide film
On 30 one side, the polyimides/metal composite laminated plates are obtained.
2 polyimides of embodiment/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, differs only in the first Thermocurable polyimide film of the present embodiment
Thickness is 8 microns.
3 polyimides of embodiment/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, differ only in the first Thermocurable polyimide film of the present embodiment by
Made by PI-6.
4 polyimides of embodiment/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, differ only in the first Thermocurable polyimide film of the present embodiment by
Made by PI-6, and its thickness is 5 microns.
5 polyimides of embodiment/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, differ only in the present embodiment the first thermoplastic polyimide film and
As made by TPI-2, the first Thermocurable polyimide film is as made by PI-6, and the first thermosetting for second thermoplastic polyimide film
Property polyimide film thickness be 20 microns.
6 polyimides of embodiment/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, differ only in the present embodiment the first thermoplastic polyimide film and
As made by TPI-2, the first Thermocurable polyimide film is as made by PI-6, and the first thermosetting for second thermoplastic polyimide film
Property polyimide film thickness be 8 microns.
7 polyimides of embodiment/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, differ only in the present embodiment the first thermoplastic polyimide film and
As made by TPI-3, the first Thermocurable polyimide film is as made by PI-6, and the first thermosetting for second thermoplastic polyimide film
Property polyimide film thickness be 8 microns.
8 polyimides of embodiment/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, differ only in the present embodiment the first thermoplastic polyimide film and
As made by TPI-4, the first Thermocurable polyimide film is as made by PI-6, and the first thermosetting for second thermoplastic polyimide film
Property polyimide film thickness be 8 microns.
9 polyimides of embodiment/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, differ only in the first Thermocurable polyimide film of the present embodiment by
Made by PI-4.
10 polyimides of embodiment/metal composite laminated plates
As shown in Fig. 2 the polyimides of the present embodiment/metal composite laminated plates include Copper Foil 10A, the first thermoplasticity polyamides
Imines film 20A, the first Thermocurable polyimide film 30A and the second thermoplastic polyimide film 40A.The first thermoplasticity polyamides is sub-
Amine film 20A, the first Thermocurable polyimide film 30A and second thermoplastic polyimide film 40A sequentially recline and are overlapped in this
On Copper Foil 10A.
As shown in Fig. 1 and 2, the Copper Foil 10A of the polyimides/metal composite laminated plates of the present embodiment is equivalent to embodiment 1
Polyimides/metal composite laminated plates the first Copper Foil 10.
11 polyimides of embodiment/metal composite laminated plates
As shown in figures 1 and 3, the present embodiment is roughly the same with the polyimides/metal composite laminated plates of embodiment 1, this reality
Apply example is with the difference of embodiment 1：The polyimides of the present embodiment/metal composite laminated plates include the 3rd thermoplasticity polyamides
Imines film 60, the 3rd thermoplastic polyimide film 60 is stacked and placed on second Copper Foil 50 and second thermoplastic polyimide film 40
Between.
12 polyimides of embodiment/metal composite laminated plates
As shown in figs. 3 and 4, the present embodiment is roughly the same with the polyimides/metal composite laminated plates of embodiment 11, this reality
Apply example is with the difference of embodiment 11：The polyimides of the present embodiment/metal composite laminated plates include the second thermosetting polyamides
Imines film 70, the second Thermocurable polyimide film 70 is stacked and placed on the 3rd thermoplastic polyimide film 60 and second thermoplasticity
Between polyimide film 40.
13 polyimides of embodiment/metal composite laminated plates
As shown in figs. 4 and 5, the present embodiment is roughly the same with the polyimides/metal composite laminated plates of embodiment 12, this reality
Apply example is with the difference of embodiment 12：The polyimides of the present embodiment/metal composite laminated plates include the 4th thermoplasticity polyamides
Imines film 80, the 4th thermoplastic polyimide film 80 is stacked and placed on the second Thermocurable polyimide film 70 and second thermoplasticity
Between polyimide film 40.
1 polyimides of comparative example/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with embodiment 1, differ only in the first Thermocurable polyimide film of this comparative example by
Made by PI-6, and the thickness of the first Thermocurable polyimide film is 8 microns.
2 polyimides of comparative example/metal composite laminated plates and preparation method thereof
As shown in fig. 6, the polyimides of this comparative example/metal composite laminated plates include Copper Foil 10B, TPI
Film 20B and Thermocurable polyimide film 30B.The two sides of thermoplastic polyimide film 20B respectively with Copper Foil 10B and the heat
Solidity polyimide film 30B connects.Wherein, the thickness of thermoplastic polyimide film 20B is 2 to 3 microns, the thermosetting polyamides
The thickness of imines film 30B is 17 to 18 microns.
As shown in Fig. 1 and 6, the Copper Foil 10B of the polyimides/metal composite laminated plates of this comparative example, thermoplasticity polyamides are sub-
Amine film 20B and Thermocurable polyimide film 30B, the of the polyimides that it is respectively equivalent to embodiment 1/metal composite laminated plates
One Copper Foil 10, the first thermoplastic polyimide film 20 and the first Thermocurable polyimide film 30.
As shown in fig. 6, the polyimides of this comparative example/metal composite laminated plates preparation method is as described below.
First TPI-1 is coated on the one side of Copper Foil 10B, form TPI precursor layer；Again by PI-
1 coats the TPI precursor layer away from the one side of Copper Foil 10B, forms Thermocurable polyimide forerunner
Nitride layer.
Then, with 80 DEG C to 150 DEG C except solvent temperature removes the TPI precursor layer and the thermosetting
Contained solvent, i.e. METHYLPYRROLIDONE in polyimides precursor layer.
Thereafter, by the TPI precursor layer and the Thermocurable polyimide through removal solvent through removing solvent
Precursor layer is sequentially heated to 160 DEG C to 190 DEG C of temperature, 190 DEG C to 300 DEG C of temperature and 300 DEG C to 350 DEG C of temperature simultaneously
Spend to carry out cyclization；After the cyclization terminates, this is cyclized through removing the TPI precursor layer of solvent
It is thermoplastic polyimide film 20B, this is through removing the Thermocurable polyimide precursor layer cyclisation of solvent for the thermosetting is poly-
Acid imide film 30B, obtains the polyimides/metal composite laminated plates.
3 polyimides of comparative example/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 2, and the Thermocurable polyimide film for differing only in this comparative example is PI-2
It is made.
4 polyimides of comparative example/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 2, and the Thermocurable polyimide film for differing only in this comparative example is PI-3
It is made.
5 polyimides of comparative example/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 2, and the Thermocurable polyimide film for differing only in this comparative example is PI-4
It is made.
6 polyimides of comparative example/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 2, and the Thermocurable polyimide film for differing only in this comparative example is PI-5
It is made.
7 polyimides of comparative example/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 2, and the Thermocurable polyimide film for differing only in this comparative example is PI-6
It is made.
8 polyimides of comparative example/metal composite laminated plates and preparation method thereof
As shown in fig. 7, the polyimides of this comparative example/metal composite laminated plates include Copper Foil 10C, Thermocurable polyimide
Film 30C and thermoplastic polyimide film 40C.The two sides of Thermocurable polyimide film 30C respectively with Copper Foil 10C and the heat
Plastic polyimide film 40C connects.Wherein, the thickness of thermoplastic polyimide film 40C is 2 to 3 microns, first thermosetting
The thickness of polyimide film 30C is 17 to 18 microns.
As shown in Fig. 1 and 7, the Copper Foil 10C of the polyimides/metal composite laminated plates of this comparative example, thermosetting polyamides are sub-
Amine film 30C and thermoplastic polyimide film 40C, the of the polyimides that it is respectively equivalent to embodiment 1/metal composite laminated plates
One Copper Foil 10, the first Thermocurable polyimide film 30 and the second thermoplastic polyimide film 40.
As shown in fig. 7, the polyimides of this comparative example/metal composite laminated plates preparation method is as described below.
First PI-3 is coated on the one side of Copper Foil 10C, form Thermocurable polyimide precursor layer；Again by TPI-
1 coats the Thermocurable polyimide precursor layer away from the one side of Copper Foil 10C, forms TPI forerunner
Nitride layer.
Then, with 80 DEG C to 150 DEG C except solvent temperature removes the Thermocurable polyimide precursor layer and the thermoplasticity
Contained solvent, i.e. METHYLPYRROLIDONE in polyimides precursor layer.
Afterwards, by the Thermocurable polyimide precursor layer and the TPI through removal solvent through removing solvent
Precursor layer is sequentially heated to 160 DEG C to 190 DEG C of temperature, 190 DEG C to 300 DEG C of temperature and 300 DEG C to 350 DEG C of temperature simultaneously
Spend to carry out cyclization；After the cyclization terminates, this is cyclized through removing the Thermocurable polyimide precursor layer of solvent
It is Thermocurable polyimide film 30C, the TPI precursor layer cyclisation through removing solvent is the thermoplastic poly
Acid imide film 40C, obtains the polyimides/metal composite laminated plates.
9 polyimides of comparative example/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 8, and the Thermocurable polyimide film for differing only in this comparative example is PI-4
It is made.
10 polyimides of comparative example/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 8, and the Thermocurable polyimide film for differing only in this comparative example is PI-5
It is made.
11 polyimides of comparative example/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 8, differs only in the Thermocurable polyimide film and thermoplastic of this comparative example
Property polyimide film is respectively made by PI-5 and TPI-2.
12 polyimides of comparative example/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 8, differs only in the Thermocurable polyimide film and thermoplastic of this comparative example
Property polyimide film is respectively made by PI-6 and TPI-3.
13 polyimides of comparative example/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 8, differs only in the Thermocurable polyimide film and thermoplastic of this comparative example
Property polyimide film is respectively made by PI-6 and TPI-4.
Analysis result and discussion
This analysis result with discuss involved by analysis method it is as described below.
Glass transition temperature (Tg)：So that the Pyris Diamond Dynamic Mechanical Analyzers of PerkinElmer companies are measured
, thermograde is 10 DEG C/min.
Thermal coefficient of expansion (coefficient of thermal expansion, CTE)：With PerkinElmer companies
Pyris Diamond thermomechanical analyzers are measured and obtained, and thermograde is 10 DEG C/min.
Aqueous vapor penetrance (water vapor transmission rate, WVTR)：With aqueous vapor penetrance analyzer amount
Survey, the aqueous vapor penetrance analyzer is the PERMATRAN-W Model 3/61 of Mocon Inc. of the U.S. (Mocon Inc.), is measured
Parameter is 40 DEG C and 90%RH.
Peel strength (peeling strength)：According to IPC-TM-650 2.4.9.
Dimensional stability (dimensional stability)：According to the method B and method C of IPC-TM-650 2.2.4.
Soldering resistance (solder resistance) is tested：According to IPC-TM-650 2.4.13, the condition that measures is 300 DEG C/
30 seconds.
Additionally, this analysis result is also related to the delamination caused by cyclization and albinism with discussion.
As shown in table 1,2 and Fig. 1, the first Thermocurable polyimide film 30 of embodiment 1 to 9 and the first thermoplasticity polyamides are sub-
Between amine film 20；And, there is no delamination between the second thermoplastic polyimide film 40 and the first Thermocurable polyimide film 30
And albinism, show embodiment 1 to 9 the first Thermocurable polyimide film 30 and the first thermoplastic polyimide film 20 it
Between；And, the aqueous vapor between the second thermoplastic polyimide film 40 and the first Thermocurable polyimide film 30 is moved out.Compare
The first Thermocurable polyimide film 30 and the first thermoplastic polyimide film 20 of the polyimides of example 1/metal composite laminated plates
Between；And, there is delamination between the second thermoplastic polyimide film 40 and the first Thermocurable polyimide film 30 and albefaction is existing
As showing between the first Thermocurable polyimide film 30 and the first thermoplastic polyimide film 20 of comparative example 1；And, second
Aqueous vapor between the Thermocurable polyimide film 30 of thermoplastic polyimide film 40 and first fails to be completely exhausted out.
The characteristic and its first thermoplastic poly of the polyimides/metal composite laminated plates of the comparative example 1, embodiment 1 to 4 of table 1
The raw material and thickness of acid imide film, the second thermoplastic polyimide film and the first Thermocurable polyimide film.
The characteristic of the polyimides of the embodiment 5 to 9 of table 2/metal composite laminated plates and its first thermoplastic polyimide film,
The raw material and thickness of the second thermoplastic polyimide film and the first Thermocurable polyimide film.
As shown in table 3 and Fig. 6, the thermoplastic polyimide film of the polyimides/metal composite laminated plates of comparative example 2 to 4
There is delamination and albinism between 20B and Thermocurable polyimide film 30B, and the polyimides/metal of comparative example 5 to 7 is multiple
Close laminated plates and delamination and albinism do not occur then；Further coordinate it can be seen from table 4 and 5, the thermosetting of comparative example 2 to 4 gathers
The aqueous vapor penetrance of acid imide film 30B is less than (g- μm/m of 170 grams-micron/square metre-day2- day), and the heat of comparative example 5 to 7
The aqueous vapor penetrance of solidity polyimide film 30B is more than or equal to 170g- μm/m2-day；Show that the polyamides of comparative example 5 to 7 is sub-
There is no delamination and albinism due to the water of the Thermocurable polyimide film 30B of comparative example 5 to 7 in amine/metal composite laminated plates
Gas penetrance is more than or equal to 170g- μm/m2Caused by-day.
Table 3 is denoted as the Thermocurable polyimide acid predecessor of PI-1, PI-2, PI-3, PI-4, PI-5 and PI-6 via height
The glass transition temperature of resulting Thermocurable polyimide film, thermal coefficient of expansion and aqueous vapor penetrance after temperature cyclisation
Table 4 is denoted as the TPI acid predecessor of TPI-1, TPI-2, TPI-3 and TPI-4 via high temperature cyclization
The glass transition temperature of resulting thermoplastic polyimide film, thermal coefficient of expansion, aqueous vapor penetrance afterwards.
The stripping of the polyimides of the comparative example 2 to 7 of table 5/metal composite laminated plates, albinism and its thermoplasticity polyamides are sub-
The raw material and thickness of amine film and Thermocurable polyimide film.
Further compare comparative example 2 to 4 and comparative example 5 to 7 understands, the Thermocurable polyimide film of comparative example 5 to 7
30B respectively as made by PI-4, PI-5 and PI-6, and the Thermocurable polyimide film 30B of comparative example 2 to 4 respectively by PI-1,
Made by PI-2 and PI-3；On the basis of the total mole number of the first reactive monomer and diamine monomer, PI-4, PI-5 and PI-6 institute
The first reactive monomer for containing is at least 2.7 molar percentages, and the first reactive monomer contained by PI-2 and PI-3 is low
In 2.7 molar percentages, PI-1 does not contain the first reactive monomer then.
As shown in table 6 and Fig. 7, the thermoplastic polyimide film of the polyimides/metal composite laminated plates of comparative example 8 to 13
There is no delamination and albinism between 40C and Thermocurable polyimide film 30C, further coordinate it can be seen from table 4 and 5, by
It is more than 170g- μm/m in the aqueous vapor penetrance of the thermoplastic polyimide film 40C of comparative example 8 to 132- day so that comparative example 8
It is moved out to the aqueous vapor between 13 thermoplastic polyimide film 40C and Thermocurable polyimide film 30C.
The stripping of the polyimides of the comparative example 8 to 13 of table 6/metal composite laminated plates, albinism and its thermoplasticity polyamides
The raw material and thickness of imines film and Thermocurable polyimide film.
Deduced by above-mentioned, the first Thermocurable polyimide film 30 of embodiment 1 to 9 and the first thermoplastic polyimide film
Between 20；And, there is no delamination and white between the second thermoplastic polyimide film 40 and the first Thermocurable polyimide film 30
Change phenomenon, and the first Thermocurable polyimide film 30 of the polyimides of comparative example 1/metal composite laminated plates and the first thermoplasticity
Between polyimide film 20；And, occur between the second thermoplastic polyimide film 40 and the first Thermocurable polyimide film 30
Delamination and albinism, this is due to the first Thermocurable polyimide film 30 of embodiment 1 to 9 and the second TPI
The aqueous vapor penetrance of film 40 is more than or equal to 170g- μm/m2- day, and embodiment 1 to 9 and the second thermoplastic polyimide film
Caused by 40 aqueous vapor penetrance is more than the aqueous vapor penetrance of the first Thermocurable polyimide film 30.And above-mentioned deduce by with two
On the basis of amine monomers and reactive monomer, PI-4, PI-5 containing the first more than 3.39 molar percentages reactive monomers and
PI-6, can be big by the aqueous vapor penetrance of the first Thermocurable polyimide film of embodiment 1 to 9 and the second thermoplastic polyimide film
In or equal to 170g- μm/m2-day；And contain TPI-1, TPI- of the second more than 35.89 molar percentages reactive monomers
, can be more than or equal to for the aqueous vapor penetrance of the second thermoplastic polyimide film of embodiment 1 to 9 by the 2nd, TPI-3 and TPI-4
170g-μm/m2-day。
As shown in table 1 and 2, the polyimide film/metal composite laminated plates of embodiment 1 to 9 can be by 300 DEG C/30 seconds
Soldering resistance is tested, and is shown the polyimide film/metal composite laminated plates of embodiment 1 to 9 and is had good soldering resistance.
As shown in table 1 and 2, the dimensional stability (B) of the polyimide film/metal composite laminated plates of embodiment 1 to 9
And M.D. levels off to 0, and the dimensional stability (C) of the polyimide film/metal composite laminated plates of embodiment 1 to 9 T.D.
T.D. and M.D. levels off to 0, there is good size to stabilize to show the polyimide film/metal composite laminated plates of embodiment 1 to 9
Property.
As shown in table 1 and table 2, the peel strength of the polyimide film/metal composite laminated plates of embodiment 1 to 9 is more than
0.8Kg/cm, showing the polyimide film/metal composite laminated plates of embodiment 1 to 9 has good peel strength.
In sum, by PI-4, PI-5 and PI-6 containing the first more than 3.39 molar percentages reactive monomers
With the use of TPI-1, TPI-2, TPI-3 and TPI-4 containing the second more than 35.89 molar percentages reactive monomers, reality
The the first Thermocurable polyimide film and the second thermoplastic polyimide film for applying example 1 to 9 have more than or equal to 170g- μm/m2-
The aqueous vapor penetrance of day, thus delamination and the generation of albinism are avoided, and learnt via test, the polyamides of embodiment 1 to 9
Imines film/metal composite laminated plates have good soldering resistance, dimensional stability and peel strength.
Claims (18)
1. a kind of polyimides/metal composite laminated plates, wherein including：
First metal film；
First thermoplastic polyimide film, it reclines and is overlapped on the one side of first metal film；
First Thermocurable polyimide film, it reclines and is overlapped in first thermoplastic polyimide film away from first metal
On the one side of film, and the first Thermocurable polyimide film aqueous vapor penetrance be not less than 170 grams-micron/square metre-
My god；And,
Second thermoplastic polyimide film, it reclines and is overlapped in the first Thermocurable polyimide film away from first thermoplastic
Property polyimide film one side on, and second thermoplastic polyimide film aqueous vapor penetrance be not less than it is described first heat
The aqueous vapor penetrance of solidity polyimide film；
Wherein, the first Thermocurable polyimide film is that as obtained by Thermocurable polyimide predecessor, the thermosetting gathers
Acid imide predecessor is as obtained by the first diamine monomer, the first reactive monomer and the first dianhydride monomer and described first
Reactive monomer is selected from by double (4- aminophenyls) propane of 2,2'-, double (3- amino-benzene oxygens) benzene of 1,3-, 4,4'- (1,3- Asias benzene
Base diisopropylidene) group that is constituted of diphenylamines, double (4- aminophenyls) fluorenes and the polypropyleneoxide diamines of 9,9'-, with described the
On the basis of the total mole number of one diamine monomer and first reactive monomer, the molal quantity of first reactive monomer between
Between 3.00 to 7.00 molar percentages；
First thermoplastic polyimide film and second thermoplastic polyimide film are by TPI forerunner
Thing, the TPI predecessor is by the second diamine monomer, the second reactive monomer and the second dianhydride monomer institute
It is obtained, and second reactive monomer is selected from by double (4- aminophenyls) propane of 2,2'-, 1,3- pairs (3- amino-benzene oxygens)
Double (4- aminophenyls) fluorenes of benzene, 4,4'- (1,3- phenylenes diisopropylidene) diphenylamines, 9,9'- and polypropyleneoxide diamine institute structure
Into group, on the basis of the total mole number of second diamine monomer and second reactive monomer, it is described second reaction
The molal quantity of property monomer is between 35.00 to 65.00 molar percentages.
2. polyimides as claimed in claim 1/metal composite laminated plates, wherein comprising the second metal film, second gold medal
Category film reclines and is overlapped in second thermoplastic polyimide film away from the one side of the first Thermocurable polyimide film.
3. polyimides as claimed in claim 2/metal composite laminated plates, wherein comprising the 3rd thermoplastic polyimide film,
3rd thermoplastic polyimide film is stacked and placed between second metal film and second thermoplastic polyimide film.
4. polyimides as claimed in claim 3/metal composite laminated plates, wherein comprising the second Thermocurable polyimide film,
It is sub- with the second thermoplasticity polyamides that the second Thermocurable polyimide film is stacked and placed on the 3rd thermoplastic polyimide film
Between amine film.
5. polyimides as claimed in claim 4/metal composite laminated plates, wherein comprising the 4th thermoplastic polyimide film,
It is sub- with the second thermoplasticity polyamides that 4th thermoplastic polyimide film is stacked and placed on the second Thermocurable polyimide film
Between amine film.
6. the polyimides as any one of claim 1 to 5/metal composite laminated plates, wherein second thermoplasticity
The aqueous vapor penetrance of polyimide film is not less than 200 grams-micron/square metre-day.
7. the polyimides as any one of claim 1 to 5/metal composite laminated plates, wherein first thermosetting
The aqueous vapor penetrance of polyimide film is not less than 200 grams-micron/square metre-day.
8. the polyimides as any one of claim 1 to 5/metal composite laminated plates, wherein first thermoplasticity
The overall aqueous vapor penetrance of polyimide film, the first Thermocurable polyimide film and second thermoplastic polyimide film
It is not less than between 180 grams-micron/square metre-day.
9. the polyimides as any one of claim 1 to 5/metal composite laminated plates, wherein first thermoplasticity
The gross thickness of polyimide film, the first Thermocurable polyimide film and second thermoplastic polyimide film is micro- between 9
Rice is between 25 microns.
10. a kind of preparation method of polyimides/metal composite laminated plates, its step is included：
First diamine monomer, the first reactive monomer and the first dianhydride monomer are polymerized in the first solvent, to obtain thermosetting
Property polyimides predecessor, first reactive monomer is selected from by 2,2'- double (4- aminophenyls) propane, 1, double (the 3- ammonia of 3-
Phenoxyl) benzene, 4,4'- (1,3- phenylenes diisopropylidene) diphenylamines, double (4- aminophenyls) fluorenes of 9,9'- and polyoxypropylene
The group that diamines is constituted, and on the basis of the total mole number of first diamine monomer and first reactive monomer, institute
The molal quantity of the first reactive monomer is stated between 3.00 to 7.00 molar percentages；
Second diamine monomer, the second reactive monomer and the second dianhydride monomer are polymerized in the second solvent, to obtain thermoplastic
Property polyimides predecessor, second reactive monomer is selected from by 2,2'- double (4- aminophenyls) propane, 1, double (the 3- ammonia of 3-
Phenoxyl) benzene, 4,4'- (1,3- phenylenes diisopropylidene) diphenylamines, double (4- aminophenyls) fluorenes of 9,9'- and polyoxypropylene
The group that diamines is constituted, and on the basis of the total mole number of second diamine monomer and second reactive monomer, institute
The molal quantity of the second reactive monomer is stated between 35.00 to 65.00 molar percentages；
The TPI predecessor is coated with the one side of the first Copper Foil, to form the first TPI
Precursor layer；
The Thermocurable polyimide predecessor is coated with the first TPI precursor layer away from described first
On the one side of Copper Foil, to be molded the first Thermocurable polyimide precursor layer；
The TPI predecessor is coated with the first Thermocurable polyimide precursor layer away from described first
On the one side of TPI precursor layer, to be molded the second TPI precursor layer；And,
By the first TPI precursor layer, the first Thermocurable polyimide precursor layer and described second
The cyclisation of TPI precursor layer is the first thermoplastic polyimide film, the first Thermocurable polyimide film and the second heat
Plastic polyimide film, obtains the polyimides/metal composite laminated plates.
The preparation method of 11. polyimides as claimed in claim 10/metal composite laminated plates, wherein, by the described first heat
Before plastic polyimide precursor layer, the first Thermocurable polyimide precursor layer and second TPI
It is first thermoplastic polyimide film, the first Thermocurable polyimide film and second thermoplasticity to drive nitride layer cyclisation
Polyimide film, further includes the step of obtain the polyimides/metal composite laminated plates：
By the first TPI precursor layer, the first Thermocurable polyimide precursor layer and described second
The cyclisation of TPI precursor layer is first thermoplastic polyimide film, the first Thermocurable polyimide film
And the step of the second thermoplasticity polyamides Asia thing film；And,
Press the second Copper Foil in second thermoplastic polyimide film away from the first Thermocurable polyimide film side
On face, the step of obtain the polyimides/metal composite laminated plates.
The preparation method of the 12. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, by described
One TPI precursor layer, the first Thermocurable polyimide precursor layer and the second thermoplasticity polyamides are sub-
The cyclisation of amine precursor layer is first thermoplastic polyimide film, the first Thermocurable polyimide film and second heat
Plastic polyimide film, further includes the step of obtain the polyimides/metal composite laminated plates：
At 80 DEG C to 150 DEG C except under solvent temperature, the first TPI precursor layer, first heat are removed
Solvent contained by solidity polyimides precursor layer and the second TPI precursor layer, obtains molten through removing
First TPI precursor layer of agent, through remove solvent the first Thermocurable polyimide precursor layer and through removal
The step of second TPI precursor layer of solvent；And
By it is described through remove solvent the first TPI precursor layer, it is described through remove solvent the first thermosetting gather
Acid imide precursor layer and the second TPI precursor layer through removing solvent are sequentially heated to 160 DEG C simultaneously
Temperature, 190 DEG C to 300 DEG C of temperature and 300 DEG C to 350 DEG C of temperature to 190 DEG C, are first thermoplastic to be cyclized respectively
Property polyimide film, the first Thermocurable polyimide film and second thermoplastic polyimide film, obtain the polyamides
The step of imines/metal composite laminated plates.
The preparation method of the 13. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, by described
One diamine monomer, first reactive monomer and first dianhydride monomer are polymerized in first solvent, to obtain
In the step of Thermocurable polyimide predecessor, first diamine monomer is selected from by 3,4'- diamino-diphenyls ether, 4,
4'- diamino-diphenyls ether, p-phenylenediamine, m-phenylene diamine (MPD), 3,5- diaminobenzoic acids, 4,4'- diaminodiphenyl-methanes, 4,
Double (the 4- aminobenzene oxygen of 4'- diamino diphenyl sulfones, 3,3'- diamino diphenyl sulfones, 4,4'- diamino diphenyl sulfides, 1,3-
Base) benzene, double (4- amino-benzene oxygens) benzene of 1,4-, double (4- the amino-benzene oxygens)-biphenyl of 4,4-, double [4- (the 4- aminobenzene oxygen of 2,2'-
Base) phenyl] propane, 2,2'- double [4- (3- amino-benzene oxygens) phenyl] propane, 2,2'- dimethyl -4,4'- benzidines, 3,
3'- dimethyl -4,4'- benzidines, 2,6- diamino-pyridines, 4,4'- (1,4- phenylenes diisopropylidene) diphenylamines, drop
The group that bornylane dimethylamine and combinations thereof is constituted.
The preparation method of the 14. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, by described
One diamine monomer, first reactive monomer and first dianhydride monomer are polymerized in first solvent, to obtain
In the step of Thermocurable polyimide predecessor, first dianhydride monomer is selected from by equal benzene tertacarbonic acid's dianhydride, 3,3',
4,4'- biphenyl tetracarboxylic dianhydrides, 3,3',4,4' benzophenone tetracarboxylic dianhydride, the phthalic acid dianhydride of 4,4'- oxygen two, 3,3',
4,4'- diphenyl sulfones tetracarboxylic dianhydride, ethylene glycol-bis- trimellitic anhydrides, 1,2,3,4- butane tetracarboxylics acid dianhydride, 1,2,3,4- rings
The group that pentane tetracarboxylic dianhydride and combinations thereof is constituted.
The preparation method of the 15. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, by described
One diamine monomer, first reactive monomer and first dianhydride monomer are polymerized in first solvent, to obtain
In the step of Thermocurable polyimide predecessor, first solvent be selected from by tetrahydrofuran, DMF,
The group that DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, gamma-butyrolacton and combinations thereof are constituted.
The preparation method of the 16. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, by described
Two diamine monomers, second reactive monomer and second dianhydride monomer are polymerized in second solvent, to obtain
In the step of TPI predecessor, second diamine monomer is selected from by 3,4'- diamino-diphenyls ether, 4,
4'- diamino-diphenyls ether, p-phenylenediamine, m-phenylene diamine (MPD), 3,5- diaminobenzoic acids, 4,4'- diaminodiphenyl-methanes, 4,
Double (the 4- aminobenzene oxygen of 4'- diamino diphenyl sulfones, 3,3'- diamino diphenyl sulfones, 4,4'- diamino diphenyl sulfides, 1,3-
Base) benzene, double (4- amino-benzene oxygens) benzene of 1,4-, double (4- the amino-benzene oxygens)-biphenyl of 4,4-, double [4- (the 4- aminobenzene oxygen of 2,2'-
Base) phenyl] propane, 2,2'- double [4- (3- amino-benzene oxygens) phenyl] propane, 2,2'- dimethyl -4,4'- benzidines, 3,
3'- dimethyl -4,4'- benzidines, 2,6- diamino-pyridines, 4,4'- (1,4- phenylenes diisopropylidene) diphenylamines, drop
The group that bornylane dimethylamine and combinations thereof is constituted.
The preparation method of the 17. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, by described
Two diamine monomers, second reactive monomer and second dianhydride monomer are polymerized in second solvent, to obtain
In the step of Thermocurable polyimide predecessor, second dianhydride monomer is selected from by equal benzene tertacarbonic acid's dianhydride, 3,3',
4,4'- biphenyl tetracarboxylic dianhydrides, 3,3',4,4' benzophenone tetracarboxylic dianhydride, the phthalic acid dianhydride of 4,4'- oxygen two, 3,3',
4,4'- diphenyl sulfones tetracarboxylic dianhydride, ethylene glycol-bis- trimellitic anhydrides, 1,2,3,4- butane tetracarboxylics acid dianhydride, 1,2,3,4- rings
The group that pentane tetracarboxylic dianhydride and combinations thereof is constituted.
The preparation method of the 18. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, by described
Two diamine monomers, second reactive monomer and second dianhydride monomer are polymerized in second solvent, to obtain
In the step of Thermocurable polyimide predecessor, second solvent be selected from by tetrahydrofuran, DMF,
The group that DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, gamma-butyrolacton and its mixture are constituted.
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| CN115368566A (en) * | 2022-09-02 | 2022-11-22 | 中国科学技术大学先进技术研究院 | Polyimide composite membrane with low moisture absorption rate and low thermal expansion coefficient, preparation method thereof, thermosetting polyamic acid and thermosetting polyamic acid solution |
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