CN105015099A - Polyimide/metal composite laminated plate and preparation method thereof - Google Patents
Polyimide/metal composite laminated plate and preparation method thereof Download PDFInfo
- Publication number
- CN105015099A CN105015099A CN201410178745.7A CN201410178745A CN105015099A CN 105015099 A CN105015099 A CN 105015099A CN 201410178745 A CN201410178745 A CN 201410178745A CN 105015099 A CN105015099 A CN 105015099A
- Authority
- CN
- China
- Prior art keywords
- polyimide film
- metal composite
- polyimides
- composite laminated
- precursor layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a polyimide/metal composite laminated plate and a preparation method thereof. The polyimide/metal composite laminated plate comprises first copper foil, a first thermoplastic polyimide film attached to one side face of the first copper foil, a first thermosetting polyimide membrane and a second thermoplastic polyimide film, wherein the first thermoplastic polyimide film, the first thermosetting polyimide membrane and the second thermoplastic polyimide film are attached and overlapped in sequence. Due to the fact that a glue layer is omitted, the polyimide/metal composite laminated plate can be used for a thin soft printed circuit board and has good welding resistance, size stability and stripping strength. Meanwhile, by means of the first thermosetting polyimide membrane and the second thermoplastic polyimide film with the water vapor penetration rate higher than or equal to 170g-micron/m<2>-day, the polyimide/metal composite laminated plate can avoid the delamination phenomenon and the withening phenomenon.
Description
Technical field
The present invention about a kind of polyimides/metal composite laminated plates and preparation method thereof, espespecially a kind of polyimides/metal composite laminated plates saving glue-line and preparation method thereof.
Background technology
Aromatic polyimides is because having high-temperature resistant, chemical resistance, excellent machinery and the characteristic such as electric, be used in the flexible printed wiring board (flexible printed circuitboard, FPCB) of the electronic components in the electronic product of notebook computer, consumer electronics and communication hand-held widely.
The manufacture of existing flexible printed wiring board, take polyimide film as base material, in the two sides of polyimide film respectively epoxy resin coating or acryl resin with shaping glue-line, again two metal copper foils are fitted on the two sides of polyimide film through two glue-lines respectively, obtain this flexible printed wiring board.
But the glue-line be made up of epoxy resin or acryl resin can exert an adverse impact for heat-resisting, the resistance to combustion of flexible printed wiring board, anti-ization and dimensional stability, and glue-line has suitable thickness, cannot meet the thinning tendency of flexible printed wiring board.
Summary of the invention
In view of the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of polyimides/metal composite laminated plates saving glue-line and preparation method thereof.
In order to reach aforesaid goal of the invention, the technological means that the present invention takes is a kind of polyimides/metal composite laminated plates, wherein comprises:
First metal film;
First thermoplastic polyimide film, its recline be overlapped in described first metal film a side on;
First Thermocurable polyimide film, it reclines and is overlapped on the side of described first thermoplastic polyimide film away from described first metal film, and the aqueous vapor penetrance of described first Thermocurable polyimide film is not less than 170 grams-micron/square metre-day (g-μm/m
2-day); And,
Second thermoplastic polyimide film, it reclines and is overlapped on the side of described first Thermocurable polyimide film away from described first thermoplastic polyimide film, and the aqueous vapor penetrance of described second thermoplastic polyimide film is not less than the aqueous vapor penetrance of described first Thermocurable polyimide film.
Described polyimides/metal composite laminated plates, owing to not having glue-line, can meet the trend of the slimming of flexible printed wiring board and have good soldering resistance, dimensional stability and peel strength; Meanwhile, 170g-μm/m is not less than by having
2first Thermocurable polyimide film of the aqueous vapor penetrance of-day and the second thermoplastic polyimide film, described polyimides/metal composite laminated plates can avoid the generation of delamination and albinism.
In one embodiment, described polyimides/metal composite laminated plates comprises to recline and is overlapped in described second thermoplastic polyimide film away from the second metal film on a side of described first Thermocurable polyimide film.
In another embodiment, described polyimides/metal composite laminated plates comprises the 3rd thermoplastic polyimide film, and described second metal film reclines through described 3rd thermoplastic polyimide film and is overlapped on described second thermoplastic polyimide film.
In yet another embodiment, described polyimides/metal composite laminated plates comprises the second Thermocurable polyimide film, and described 3rd thermoplastic polyimide film reclines through described second Thermocurable polyimide film and is overlapped on described second thermoplastic polyimide film.
In still another embodiment, described polyimides/metal composite laminated plates comprises the 4th thermoplastic polyimide film, and described second Thermocurable polyimide film reclines through described 4th thermoplastic polyimide film and is overlapped in described second thermoplastic polyimide film and connects.
Preferably, the aqueous vapor penetrance of described second thermoplastic polyimide film is not less than 200g-μm/m
2-day.
Preferably, the aqueous vapor penetrance of described first Thermocurable polyimide film is not less than 200g-μm/m
2-day.
Preferably, the gross thickness of described first thermoplastic polyimide film, described first Thermocurable polyimide film and described second thermoplastic polyimide film is between 9 microns (μm) to 25 microns (μm).
Preferably, the aqueous vapor penetrance of described first thermoplastic polyimide film, described first Thermocurable polyimide film and described second thermoplastic polyimide film entirety is not less than 180g-μm/m
2-day.
In order to reach aforesaid goal of the invention, the technological means that the present invention takes is the preparation method of a kind of polyimides/metal composite laminated plates, and its step comprises:
By the first diamine monomer, first reactive monomer and the first dianhydride monomer are polymerized in the first solvent, to obtain Thermocurable polyimide predecessor, described first reactive monomer is selected from the group of following formation: 2, two (4-aminophenyl) propane (2 of 2'-, 2'-bis (4-aminophenyl) propane), 1, two (3-amino-benzene oxygen) benzene (1 of 3-, 3-bis (3-aminophenoxy) benzene), 4, 4'-(1, 3-diisopropyl alkylbenzene) diphenylamines (4, 4'-(1, 3-phenylenediisopropylidene) bisaniline, Bisaniline-M), 9, two (4-aminophenyl) fluorenes (9 of 9'-, 9'-bis (4-aminophenyl) fluorene), polyoxypropylene ether diamine (polyoxypropylenediamine), and with the total mole number of described diamine monomer and described reactive monomer for benchmark, the molal quantity of described first reactive monomer is between 3.00 to 7.00 molar percentages,
By the second diamine monomer, second reactive monomer and the second dianhydride monomer are polymerized in the second solvent, to obtain TPI predecessor, described second reactive monomer is selected from the group of following formation: 2, two (4-aminophenyl) propane of 2'-, 1, two (3-amino-benzene oxygen) benzene of 3-, 4, 4'-(1, 3-diisopropyl alkylbenzene) diphenylamines, 9, two (4-aminophenyl) fluorenes of 9'-and polyoxypropylene ether diamine, and with the total mole number of described second diamine monomer and described second reactive monomer for benchmark, the molal quantity of described second reactive monomer is between 35.00 to 65.00 molar percentages,
Be coated with described TPI predecessor on a side of the first Copper Foil, to form the first TPI precursor layer;
Be coated with described Thermocurable polyimide predecessor on the side of described first TPI precursor layer away from described first Copper Foil, with shaping first Thermocurable polyimide precursor layer;
Be coated with described TPI predecessor on the side of described first Thermocurable polyimide precursor layer away from described first TPI precursor layer, with shaping second TPI precursor layer; And,
Be the first thermoplastic polyimide film, the first Thermocurable polyimide film and the second thermoplastic polyimide film by described first TPI precursor layer, described first Thermocurable polyimide precursor layer and described second TPI precursor layer cyclisation, obtain described polyimides/metal composite laminated plates.
Described preparation method, can obtain the polyimides/metal composite laminated plates without glue-line, and owing to not having glue-line, described polyimides/metal composite laminated plates can have the low and good soldering resistance of thickness, dimensional stability and peel strength; In addition, by the use of described first reactive monomer and described second reactive monomer, polyimides obtained by described preparation method/metal composite laminated plates, its first Thermocurable polyimide film and the second thermoplastic polyimide film have and are more than or equal to 170g-μm/m
2the aqueous vapor penetrance of-day, then can avoid the generation of delamination and albinism.
Preferably, be described first thermoplastic polyimide film, described first Thermocurable polyimide film and described second thermoplastic polyimide film by described first TPI precursor layer, described first Thermocurable polyimide precursor layer and described second TPI precursor layer cyclisation, the step obtaining described polyimides/metal composite laminated plates comprises:
By the step that described first TPI precursor layer, described first Thermocurable polyimide precursor layer and described second TPI precursor layer cyclisation are described first thermoplastic polyimide film, described first Thermocurable polyimide film and described second thermoplastic polyimide film; And,
Pressing second Copper Foil, on the side of described second thermoplastic polyimide film away from described first Thermocurable polyimide film, obtains the step of described polyimides/metal composite laminated plates.
Preferably, be described first thermoplastic polyimide film, described first Thermocurable polyimide film and described second thermoplastic polyimide film by described first TPI precursor layer, described first Thermocurable polyimide precursor layer and described second TPI precursor layer cyclisation, the step obtaining described polyimides/metal composite laminated plates comprises:
80 DEG C to 150 DEG C desolventize temperature under, removing described first TPI precursor layer, described first Thermocurable polyimide precursor layer and the solvent contained by described second TPI precursor layer, obtaining the first TPI precursor layer through removing solvent, through removing the step of the first Thermocurable polyimide precursor layer of solvent and the second TPI precursor layer through removing solvent; And
Described the first TPI precursor layer through removing solvent, described the first Thermocurable polyimide precursor layer through removing solvent and described the second TPI precursor layer through removing solvent are sequentially heated to the temperature of 160 DEG C to 190 DEG C simultaneously, the temperature of the temperature of 190 DEG C to 300 DEG C and 300 DEG C to 350 DEG C is described first thermoplastic polyimide film, described first Thermocurable polyimide film and described second TPI with cyclisation respectively, obtain the step of described polyimides/metal composite laminated plates.
Preferably, described first diamine monomer and described second diamine monomer can be 3, 4'-diamino-diphenyl ether (3, 4'-diaminodiphenyl ether), 4, 4'-diamino-diphenyl ether (4, 4'-diaminodiphenyl ether), p-phenylenediamine (PPD) (p-phenylenediamine), m-phenylene diamine (MPD) (m-phenylenediamine), 3, 5-diaminobenzoic acid (3, 5-diaminobenzoicacid), 2, two (4-aminophenyl) propane (2 of 2'-, 2'-bis (4-aminophenyl) propane), 4, 4'-diaminodiphenyl-methane (4, 4'-diaminodiphenyl methane), 4, 4'-diamino diphenyl sulfone (4, 4'-diaminodiphenyl sulfone), 3, 3'-diamino diphenyl sulfone (3, 4'-diaminodiphenyl sulfone), 4, 4'-diamino diphenyl sulfide (4, 4'-diaminodiphenyl sulfide), 1, two (4-amino-benzene oxygen) benzene (1 of 3-, 3-bis (4-aminophenoxy) benzene), 1, two (3-amino-benzene oxygen) benzene (1 of 3-, 3-bis (3-aminophenoxy) benzene), 1, two (4-amino-benzene oxygen) benzene (1 of 4-, 4-bis (4-aminophenoxy) benzene), 4, two (4-the amino-benzene oxygen)-biphenyl (4 of 4-, 4-bis (3-aminophenoxy) biphenyl), 2, two [4-(4-amino-benzene oxygen) phenyl] propane (2 of 2'-, 2'-bis [4-(4-aminophenoxy) phenyl] propane), 2, two [4-(the 3-amino-benzene oxygen benzene) base] propane (2 of 2'-, 2'-bis [4-(3-aminophenoxy) pheny] propane), 2, 2'-dimethyl-4, 4'-benzidine (2, 2'-dimethyl-4, 4'-diaminobiphenyl), 3, 3'-dimethyl-4, 4'-benzidine (3, 3'-dimethyl-4, 4'-diaminobiphenyl), 3, 3'-dialkyl-4, 4'-benzidine (3, 3 '-dihydroxybiphenyl-4, 4 '-diamino), 9, two (4-aminophenyl) fluorenes (9 of 9'-, 9'-bis (4-aminophenyl) fluorene), 2, two (4-[3-amino-benzene oxygen] phenyl) sulfone (2 of 2'-, 2 '-bis (4-(3-aminophenoxy) phenyl) sulfon), 2, 6-di-amino-pyrimidine (2, 6-diaminopyridine), polypropylene ether diamines (polyoxypropylenediamine), 4, 4'-(1, 3-diisopropyl alkylbenzene) diphenylamines (4, 4'-(1, 3-phenylenediisopropylidene) bisaniline, Bisaniline-M), 4, 4'-(1, 4-diisopropyl alkylbenzene) diphenylamines (4, 4'-(1, 4-phenylenediisopropylidene) bisaniline, Bisaniline-P), bornylane diamines (norbornane dimethylamine, NBDA) and combination, but not as limit.
It is further preferred that described polypropylene ether diamines is purchased from the group of following formation:
d230,
d400 and
d2000.
Preferably, described first dianhydride monomer and described second dianhydride monomer can be the equal tetracarboxylic dianhydride of benzene (pyromellitic dianhydride), 3, 3', 4, 4'-biphenyl tetracarboxylic dianhydride (3, 3', 4, 4'-biphenyl tetracarboxylic dianhydride), 3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride (3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride), 4, 4'-oxygen two phthalic acid dianhydride (4, 4'-oxydiphthalic dianhydride), 3, 3', 4, 4'-diphenyl sulfone tetracarboxylic dianhydride (3, 3', 4, 4'-diphenylsulfone tetracarboxylic dianhydride), 2, 2'-two (3, 4-dicarboxyphenyi) HFC-236fa (2, 2'-bis (4-carboxyphenyl) hexafluoropropane), ethylene glycol-bis-trimellitic anhydride (ethylene glycol-bis-trimellitate anhydride), 1, 3-dihydro-1, the sub-phenyl ester (1 of 3-dioxy-5-isobenzofuran carboxylic acid, 3-dihydro-1, 3-dioxo-5-isobenzofurancarboxylic acid phenylene ester), 1, 2, 3, 4-butane tetracarboxylic acid dianhydride (1, 2, 3, 4-butanetetracarboxylic dianhydride), 1, 2, 3, 4-pentamethylene tetracarboxylic dianhydride (1, 2, 3, 4-cyclopentanetetracarboxylicdianhydride) and combination, but not as limit.
Preferably, described first solvent and described second solvent can be oxolane (tetrahydrofuran, THF), N, dinethylformamide (N, N-dimethylformide, DMF), N, N-dimethylacetylamide (N, N-dimethylacetamide, DMAC), METHYLPYRROLIDONE (N-methyl-2-pyrrolidone, NMP), gamma-butyrolacton (γ-butyrolactone, GBL) and combination thereof, but not as limit.
Preferably, with the total mole number of described first diamine monomer and described first reactive monomer for benchmark, the molal quantity of described first reactive monomer is between 3.00 to 7.00 molar percentages.
Preferably, with the total mole number of described second diamine monomer and described second reactive monomer for benchmark, the molal quantity of described second reactive monomer is between 35.00 to 65.00 molar percentages.
Accompanying drawing explanation
Fig. 1 is the side cutaway view of the polyimides/metal composite laminated plates of embodiments of the invention 1 to 9 and comparative example 1.
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 present invention.
Fig. 7 is the side cutaway view of the polyimides/metal composite laminated plates of comparative example 8 to 13 of the present 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.
Detailed description of the invention
The preparation of preparation example 1 Thermocurable polyimide predecessor
In the four mouthfuls of reactors of 1000 milliliters passing into nitrogen, 4,4'-diamino-diphenyl ethers of the p-phenylenediamine (PPD) of 19.877 grams and 1.940 grams are dissolved in the METHYLPYRROLIDONE of 425 grams at the temperature of 25 ± 5 DEG C, obtain diamine monomer solution; Again equal for the benzene of 8.029 grams tetracarboxylic dianhydride being added this diamine monomer solution to carry out first polymerisation, after first polymerisation is abundant, obtaining the solution through being polymerized for the first time; Afterwards, by 45.60 grams 3,3', 4,4'-biphenyltetracaboxylic dianhydride in three batches secondary to add in the solution of this warp for the first time polymerization and Keep agitation 4 hours to carry out after polymerization reaction, after after polymerization reaction terminates, obtain the Thermocurable polyimide acid predecessor of this preparation example.The Thermocurable polyimide acid predecessor of this preparation example is denoted as PI-1.
The preparation of preparation example 2 Thermocurable polyimide predecessor
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 be by the p-phenylenediamine (PPD) of 19.159 grams, 1.870 grams 4,4'-diamino-diphenyl ether and the first reactive monomer dissolve in the METHYLPYRROLIDONE of 425 grams, obtain this diamine monomer solution, and equal for the benzene of 7.739 grams tetracarboxylic dianhydride is added to this diamine monomer solution to carry out first polymerisation and to obtain the first solution be polymerized of this warp.
Wherein, first reactive monomer of this preparation example is polyoxypropylene diamine monomer
d400), its use amount is 2.260 grams, and with the total mole number of p-phenylenediamine (PPD), 4,4'-diamino-diphenyl ethers and this first reactive monomer for benchmark, the content of this first reactive monomer is 2.74 molar percentages.
In addition, the Thermocurable polyimide acid predecessor of this preparation example, is denoted as PI-2.
The preparation of preparation example 3 Thermocurable polyimide predecessor
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 the p-phenylenediamine (PPD) of 18.708 grams, 4, the 4'-diamino-diphenyl ethers of 1.826 grams and the first reactive monomer are dissolved in the METHYLPYRROLIDONE of 425 grams, obtains this diamine monomer solution; Again equal for the benzene of 7.557 grams tetracarboxylic dianhydride is added to this diamine monomer solution, to carry out first polymerisation and to obtain the first solution be polymerized of this warp.
Wherein, first reactive monomer of this preparation example is polyoxypropylene diamine monomer
d400), its use amount is 3.772 grams, and with the total mole number of p-phenylenediamine (PPD), 4,4'-diamino-diphenyl ethers and this first reactive monomer for benchmark, the content of this first reactive monomer is for being 4.59 molar percentages.
In addition, the Thermocurable polyimide acid predecessor of this preparation example is denoted as PI-3.
The preparation of preparation example 4 Thermocurable polyimide predecessor
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 the p-phenylenediamine (PPD) of 19.044 grams, 4, the 4'-diamino-diphenyl ethers of 1.858 grams and the first reactive monomer are dissolved in the METHYLPYRROLIDONE of 425 grams, obtains this diamine monomer solution; Again equal for the benzene of 7.692 grams tetracarboxylic dianhydride is added in this diamine monomer solution, to carry out first polymerisation and to obtain the first solution be polymerized of this warp.
Wherein, first reactive monomer of this preparation example is 9, two (4-aminophenyl) fluorenes of 9-, its use amount is 2.263 grams, and with p-phenylenediamine (PPD), 4, the total mole number of 4'-diamino-diphenyl ether and this first reactive monomer is benchmark, and the content of this first reactive monomer is 3.39 molar percentages.
In addition, the Thermocurable polyimide acid predecessor of this preparation example is denoted as PI-4.
The preparation of preparation example 5 Thermocurable polyimide predecessor
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 the p-phenylenediamine (PPD) of 18.490 grams, 4, the 4'-diamino-diphenyl ethers of 1.804 grams and the first reactive monomer are dissolved in the METHYLPYRROLIDONE of 425 grams, obtains this diamine monomer solution; Again equal for the benzene of 7.469 grams tetracarboxylic dianhydride is added in this diamine monomer solution, to carry out first polymerisation and to obtain the first solution be polymerized of this warp.
Wherein, first reactive monomer of this preparation example is 9, two (4-aminophenyl) fluorenes of 9-, its use amount is 3.772 grams, and with p-phenylenediamine (PPD), 4, the total mole number of 4'-diamino-diphenyl ether and this first reactive monomer is benchmark, and the content of this first reactive monomer is 5.67 molar percentages.
In addition, the Thermocurable polyimide acid predecessor of this preparation example is denoted as PI-5.
The preparation of preparation example 6 Thermocurable polyimide predecessor
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 the p-phenylenediamine (PPD) of 19.322 grams and the first reactive monomer are dissolved in the METHYLPYRROLIDONE of 425 grams, obtains this diamine monomer solution; Again equal for the benzene of 7.512 grams tetracarboxylic dianhydride is added in this diamine monomer solution, to carry out first polymerisation and to obtain the first solution be polymerized of this warp.
Wherein, first reactive monomer of this preparation example comprises polyethenoxy ether diamine monomer
and 9 D400), two (4-aminophenyl) fluorenes of 9-, the use amount of polyethenoxy ether diamine monomer is 2.057 grams, 9, the use amount of two (4-aminophenyl) fluorenes of 9-is 2.667 grams, and with the total mole number of p-phenylenediamine (PPD) and this first reactive monomer for benchmark, the content of this first reactive monomer is 6.50 molar percentages.
In addition, the Thermocurable polyimide predecessor of this preparation example is denoted as PI-6.
The preparation of preparation example 7 TPI predecessor
In the four mouthfuls of reactors of 1000 milliliters passing into nitrogen, the p-phenylenediamine (PPD) of 5.515 grams and the second reactive monomer are dissolved in the METHYLPYRROLIDONE of 425 grams at the temperature of 25 ± 5 DEG C, obtain diamine monomer solution; Again by 45.60 grams 3,3', 4,4'-biphenyltetracaboxylic dianhydride in three batches secondary to add in this diamine monomer solution and Keep agitation 4 hours to carry out polymerisation, after polymerisation terminates, obtain the TPI predecessor of this preparation example.The TPI predecessor of this preparation example is denoted as TPI-1.
Wherein, second reactive monomer of this preparation example is two (3-amino-benzene oxygen) benzene of 1,3-, and its use amount is 27.693 grams, and with the total mole number of p-phenylenediamine (PPD) and this second reactive monomer for benchmark, the content of this second reactive monomer is 65.00 molar percentages.
The preparation of preparation example 8 TPI predecessor
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 the p-phenylenediamine (PPD) of 5.516 grams and this second reactive monomer are dissolved at the temperature of 25 ± 5 DEG C in the METHYLPYRROLIDONE of 425 grams, obtains this diamine monomer solution.
Wherein, second reactive monomer of this preparation example comprises 4,4'-(1,3-diisopropyl alkylbenzene) diphenylamines and 2, two (4-aminophenyl) propane of 2'-, 4,4'-(1,3-diisopropyl alkylbenzene) use amount of diphenylamines is 23.435 grams, 2, the use amount of two (4-aminophenyl) propane of 2'-is 5.990 grams, and with the total mole number of p-phenylenediamine (PPD) and this second reactive monomer for benchmark, the content of this second reactive monomer is 61.80 molar percentages.
The TPI predecessor of this preparation example is denoted as TPI-2.
The preparation of preparation example 9 TPI predecessor
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 by 23.821 grams 1, two (4-amino-benzene oxygen) benzene of 3-and this second reactive monomer are dissolved in the METHYLPYRROLIDONE of 425 grams at the temperature of 25 ± 5 DEG C, obtain this diamine monomer solution, again equal for the benzene of 14.383 grams tetracarboxylic dianhydride is added this diamine monomer solution to carry out first polymerisation, after first polymerisation is abundant, obtain the solution through being polymerized for the first time; Afterwards, by 20.00 grams 3,3', 4,4'-biphenyltetracaboxylic dianhydride divide two batches to add in the solution of this warp for the first time polymerization and Keep agitation 4 hours to carry out after polymerization reaction, after after polymerization reaction terminates, obtain the TPI acid predecessor of this preparation example.
Wherein, second reactive monomer of this preparation example is 4,4'-(1,3-diisopropyl alkylbenzene) diphenylamines, its use amount is 18.735 grams, and with the total mole number of two (4-amino-benzene oxygen) benzene of 1,3-and this second reactive monomer for benchmark, the content of this second reactive monomer is 35.87 molar percentages.
In addition, the TPI predecessor of this preparation example is denoted as TPI-3.
The preparation of preparation example 10 TPI predecessor
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 by 18.196 grams 1, two (4-amino-benzene oxygen) benzene of 3-and this second reactive monomer are dissolved in the METHYLPYRROLIDONE of 425 grams at the temperature of 25 ± 5 DEG C, obtain this diamine monomer solution, again equal for the benzene of 10.466 grams tetracarboxylic dianhydride is added this diamine monomer solution to carry out first polymerisation, after first polymerisation is abundant, obtain the solution through being polymerized for the first time; Afterwards, by 22.00 grams 3,3', 4,4'-biphenyltetracaboxylic dianhydride divide two batches to add in the solution of this warp for the first time polymerization and Keep agitation 4 hours to carry out after polymerization reaction, after after polymerization reaction terminates, obtain the TPI acid predecessor of this preparation example.
Wherein, second reactive monomer of this preparation example is 2', two (4-aminophenyl) propane of 2-, its use amount is 25.581 grams, and with 1, the total mole number of two (4-amino-benzene oxygen) benzene of 3-and this second reactive monomer is benchmark, and the content of this second reactive monomer is 50.00 molar percentages.
In addition, the TPI predecessor of this preparation example is denoted as TPI-4.
Embodiment 1 polyimides/metal composite laminated plates and preparation method thereof
As shown in Figure 1, the polyimides/metal composite laminated plates of the present embodiment comprises the first Copper Foil 10, first thermoplastic polyimide film 20, first Thermocurable polyimide film 30, second thermoplastic polyimide film 40 and the second Copper Foil 50.This first thermoplastic polyimide film 20, this first Thermocurable polyimide film 30 and this second thermoplastic polyimide film 40 sequentially recline and are overlapped between this first Copper Foil 10 and this second Copper Foil 50, this first thermoplastic polyimide film 20 connects with this first Copper Foil 10, and this second thermoplastic polyimide film 40 connects with this second Copper Foil 50.Wherein, the thickness of this first thermoplastic polyimide film 20 and this second thermoplastic polyimide film 40 is 2 microns, and the thickness of this first Thermocurable polyimide film 30 is 15 microns.
As shown in Figure 1, preparation method is as described below for the polyimides/metal composite laminated plates of the present embodiment.
First TPI-1 is coated on a side of this first Copper Foil 10, form the first TPI precursor layer; Again PI-5 is coated this first TPI precursor layer away from a side of this first Copper Foil 10, form the first Thermocurable polyimide precursor layer; Again TPI-1 is coated on this first Thermocurable polyimide precursor layer side away from this first TPI precursor layer, form the second TPI precursor layer.
Then, solvent contained in this first TPI precursor layer, this first Thermocurable polyimide precursor layer and this second TPI precursor layer is removed, i.e. METHYLPYRROLIDONE with the temperature that desolventizes of 80 DEG C to 150 DEG C.
Afterwards, containing under the environment of nitrogen, by the first TPI precursor layer through removing solvent, through remove the first Thermocurable polyimide precursor layer of solvent and the second TPI precursor layer three through removing solvent be sequentially heated to simultaneously the temperature of 160 DEG C to 190 DEG C, the temperature of 190 DEG C to 300 DEG C and 300 DEG C to 350 DEG C temperature to carry out cyclization; After this cyclization terminates, this is this first thermoplastic polyimide film 20 through removing the first TPI precursor layer cyclisation of solvent, this is this first Thermocurable polyimide film 30 through removing the first Thermocurable polyimide precursor layer cyclisation of solvent, and this is this second thermoplastic polyimide film 40 through removing the second TPI precursor layer cyclisation of solvent.
Finally, by pressing-in temp, 50 to the double centner power/square centimeter (KgF/cm of this second Copper Foil 50 at 320 DEG C to 380 DEG C
2) pressing pressure under be pressed on the side of this second thermoplastic polyimide film 40 away from this first Thermocurable polyimide film 30, obtain this polyimides/metal composite laminated plates.
Embodiment 2 polyimides/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, and difference is only that the thickness of the first Thermocurable polyimide film of the present embodiment is 8 microns.
Embodiment 3 polyimides/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, and difference is only that the first Thermocurable polyimide film of the present embodiment is made by PI-6.
Embodiment 4 polyimides/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, and difference is only that the first Thermocurable polyimide film of the present embodiment is made by PI-6, and its thickness is 5 microns.
Embodiment 5 polyimides/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, difference is only that first thermoplastic polyimide film of the present embodiment and the second thermoplastic polyimide film are made by TPI-2, first Thermocurable polyimide film is made by PI-6, and the thickness of the first Thermocurable polyimide film is 20 microns.
Embodiment 6 polyimides/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, difference is only that first thermoplastic polyimide film of the present embodiment and the second thermoplastic polyimide film are made by TPI-2, first Thermocurable polyimide film is made by PI-6, and the thickness of the first Thermocurable polyimide film is 8 microns.
Embodiment 7 polyimides/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, difference is only that first thermoplastic polyimide film of the present embodiment and the second thermoplastic polyimide film are made by TPI-3, first Thermocurable polyimide film is made by PI-6, and the thickness of the first Thermocurable polyimide film is 8 microns.
Embodiment 8 polyimides/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, difference is only that first thermoplastic polyimide film of the present embodiment and the second thermoplastic polyimide film are made by TPI-4, first Thermocurable polyimide film is made by PI-6, and the thickness of the first Thermocurable polyimide film is 8 microns.
Embodiment 9 polyimides/metal composite laminated plates and preparation method thereof
The present embodiment is roughly the same with embodiment 1, and difference is only that the first Thermocurable polyimide film of the present embodiment is made by PI-4.
Embodiment 10 polyimides/metal composite laminated plates
As shown in Figure 2, the polyimides/metal composite laminated plates of the present embodiment comprises Copper Foil 10A, the first thermoplastic polyimide film 20A, the first Thermocurable polyimide film 30A and the second thermoplastic polyimide film 40A.This first thermoplastic polyimide film 20A, this first Thermocurable polyimide film 30A and this second thermoplastic polyimide film 40A sequentially recline and are overlapped on this 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 the first Copper Foil 10 of the polyimides/metal composite laminated plates of embodiment 1.
Embodiment 11 polyimides/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, and the present embodiment is with the difference of embodiment 1: this second Copper Foil 50 connects with this second thermoplastic polyimide film 40 through the 3rd thermoplastic polyimide film 60.
Embodiment 12 polyimides/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, and the present embodiment is with the difference of embodiment 11: the 3rd thermoplastic polyimide film 60 connects with this second thermoplastic polyimide film 40 through the second Thermocurable polyimide film 70.
Embodiment 13 polyimides/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, and the present embodiment is with the difference of embodiment 12: this second Thermocurable polyimide film 70 connects with this second thermoplastic polyimide film 40 through the 4th thermoplastic polyimide film 80.
Comparative example 1 polyimides/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with embodiment 1, and difference is only that the first Thermocurable polyimide film of this comparative example is made by PI-6, and the thickness of the first Thermocurable polyimide film is 8 microns.
Comparative example 2 polyimides/metal composite laminated plates and preparation method thereof
As shown in Figure 6, the polyimides/metal composite laminated plates of this comparative example comprises Copper Foil 10B, thermoplastic polyimide film 20B and Thermocurable polyimide film 30B.The two sides of this thermoplastic polyimide film 20B connect with this Copper Foil 10B and this Thermocurable polyimide film 30B respectively.Wherein, the thickness of this thermoplastic polyimide film 20B is 2 to 3 microns, and the thickness of this Thermocurable polyimide film 30B is 17 to 18 microns.
As shown in Fig. 1 and 6, Copper Foil 10B, the thermoplastic polyimide film 20B of the polyimides/metal composite laminated plates of this comparative example and Thermocurable polyimide film 30B, it is equivalent to the first Copper Foil 10, first thermoplastic polyimide film 20 and the first Thermocurable polyimide film 30 of the polyimides/metal composite laminated plates of embodiment 1 respectively.
As shown in Figure 6, preparation method is as described below for the polyimides/metal composite laminated plates of this comparative example.
First TPI-1 is coated on a side of this Copper Foil 10B, form TPI precursor layer; Again PI-1 is coated on the side of this TPI precursor layer away from this Copper Foil 10B, form Thermocurable polyimide precursor layer.
Then, solvent contained in this TPI precursor layer and this Thermocurable polyimide precursor layer is removed, i.e. METHYLPYRROLIDONE with the temperature that desolventizes of 80 DEG C to 150 DEG C.
Thereafter, the TPI precursor layer through removing solvent and the Thermocurable polyimide precursor layer through removing solvent are sequentially heated to simultaneously the temperature of 160 DEG C to 190 DEG C, the temperature of 190 DEG C to 300 DEG C and 300 DEG C to 350 DEG C temperature to carry out cyclization; After this cyclization terminates, this is this thermoplastic polyimide film 20B through removing the TPI precursor layer cyclisation of solvent, this is this Thermocurable polyimide film 30B through removing the Thermocurable polyimide precursor layer cyclisation of solvent, obtains this polyimides/metal composite laminated plates.
Comparative example 3 polyimides/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 2, and difference is only that the Thermocurable polyimide film of this comparative example is that PI-2 is made.
Comparative example 4 polyimides/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 2, and difference is only that the Thermocurable polyimide film of this comparative example is that PI-3 is made.
Comparative example 5 polyimides/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 2, and difference is only that the Thermocurable polyimide film of this comparative example is that PI-4 is made.
Comparative example 6 polyimides/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 2, and difference is only that the Thermocurable polyimide film of this comparative example is that PI-5 is made.
Comparative example 7 polyimides/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 2, and difference is only that the Thermocurable polyimide film of this comparative example is that PI-6 is made.
Comparative example 8 polyimides/metal composite laminated plates and preparation method thereof
As shown in Figure 7, the polyimides/metal composite laminated plates of this comparative example comprises Copper Foil 10C, Thermocurable polyimide film 30C and thermoplastic polyimide film 40C.The two sides of this Thermocurable polyimide film 30C connect with this Copper Foil 10C and this thermoplastic polyimide film 40C respectively.Wherein, the thickness of this thermoplastic polyimide film 40C is 2 to 3 microns, and the thickness of this first Thermocurable polyimide film 30C is 17 to 18 microns.
As shown in Fig. 1 and 7, Copper Foil 10C, the Thermocurable polyimide film 30C of the polyimides/metal composite laminated plates of this comparative example and thermoplastic polyimide film 40C, it is equivalent to the first Copper Foil 10, first Thermocurable polyimide film 30 and the second thermoplastic polyimide film 40 of the polyimides/metal composite laminated plates of embodiment 1 respectively.
As shown in Figure 7, preparation method is as described below for the polyimides/metal composite laminated plates of this comparative example.
First PI-3 is coated on a side of this Copper Foil 10C, form Thermocurable polyimide precursor layer; Again TPI-1 is coated on the side of this Thermocurable polyimide precursor layer away from this Copper Foil 10C, form TPI precursor layer.
Then, solvent contained in this Thermocurable polyimide precursor layer and this TPI precursor layer is removed, i.e. METHYLPYRROLIDONE with the temperature that desolventizes of 80 DEG C to 150 DEG C.
Afterwards, the Thermocurable polyimide precursor layer through removing solvent and the TPI precursor layer through removing solvent are sequentially heated to simultaneously the temperature of 160 DEG C to 190 DEG C, the temperature of 190 DEG C to 300 DEG C and 300 DEG C to 350 DEG C temperature to carry out cyclization; After this cyclization terminates, this is this Thermocurable polyimide film 30C through removing the Thermocurable polyimide precursor layer cyclisation of solvent, this is this thermoplastic polyimide film 40C through removing the TPI precursor layer cyclisation of solvent, obtains this polyimides/metal composite laminated plates.
Comparative example 9 polyimides/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 8, and difference is only that the Thermocurable polyimide film of this comparative example is made by PI-4.
Comparative example 10 polyimides/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 8, and difference is only that the Thermocurable polyimide film of this comparative example is made by PI-5.
Comparative example 11 polyimides/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 8, and difference is only that the Thermocurable polyimide film of this comparative example and thermoplastic polyimide film are respectively made by PI-5 and TPI-2.
Comparative example 12 polyimides/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 8, and difference is only that the Thermocurable polyimide film of this comparative example and thermoplastic polyimide film are respectively made by PI-6 and TPI-3.
Comparative example 13 polyimides/metal composite laminated plates and preparation method thereof
This comparative example is roughly the same with comparative example 8, and difference is only that the Thermocurable polyimide film of this comparative example and thermoplastic polyimide film are respectively made by PI-6 and TPI-4.
Analysis result and discussion
This analysis result is as described below with the analytical method involved by discussing.
Glass transition temperature (Tg): measure with the Pyris Diamond Dynamic Mechanical Analyzer of PerkinElmer company and obtain, thermograde is 10 DEG C/min.
Thermal coefficient of expansion (coefficient of thermal expansion, CTE): measure with the Pyris Diamond thermomechanical analyzer of PerkinElmer company and obtain, thermograde is 10 DEG C/min.
Aqueous vapor penetrance (water vapor transmission rate, WVTR): measure with aqueous vapor penetrance analyzer, this aqueous vapor penetrance analyzer is the PERMATRAN-W Model3/61 of Mocon Inc. of the U.S. (Mocon Inc.), and measurement parameters is 40 DEG C and 90%RH.
Peel strength (peeling strength): according to IPC-TM-6502.4.9.
Dimensional stability (dimensional stability): according to method B and the method C of IPC-TM-6502.2.4.
Soldering resistance (solder resistance) is tested: according to IPC-TM-6502.4.13, measurement condition is 300 DEG C/30 seconds.
In addition, this analysis result also relates to the delamination and albinism that cyclization causes with discussing.
As table 1,2 and Fig. 1 shown in, between the first Thermocurable polyimide film 30 of embodiment 1 to 9 and the first thermoplastic polyimide film 20; And, there is not delamination and albinism between the second thermoplastic polyimide film 40 and the first Thermocurable polyimide film 30, between the first Thermocurable polyimide film 30 of display embodiment 1 to 9 and the first thermoplastic polyimide film 20; And the aqueous vapor between the second thermoplastic polyimide film 40 and the first Thermocurable polyimide film 30 is discharged.Between first Thermocurable polyimide film 30 of the polyimides/metal composite laminated plates of comparative example 1 and the first thermoplastic polyimide film 20; And, there is delamination and albinism between the second thermoplastic polyimide film 40 and the first Thermocurable polyimide film 30, between the first Thermocurable polyimide film 30 of display comparative example 1 and the first thermoplastic polyimide film 20; And the aqueous vapor between the second thermoplastic polyimide film 40 and the first Thermocurable polyimide film 30 fails to discharge completely.
The raw material of the characteristic of the polyimides/metal composite laminated plates of table 1 comparative example 1, embodiment 1 to 4 and its first thermoplastic polyimide film, the second thermoplastic polyimide film and the first Thermocurable polyimide film and thickness.
The raw material of the characteristic of the polyimides/metal composite laminated plates of table 2 embodiment 5 to 9 and its first thermoplastic polyimide film, the second thermoplastic polyimide film and the first Thermocurable polyimide film and thickness.
As shown in table 3 and Fig. 6, between the thermoplastic polyimide film 20B of the polyimides/metal composite laminated plates of comparative example 2 to 4 and Thermocurable polyimide film 30B, delamination and albinism occurring, then there is not delamination and albinism in the polyimides/metal composite laminated plates of comparative example 5 to 7; Further cooperation is with reference to table 4 and 5 known, and the aqueous vapor penetrance of the Thermocurable polyimide film 30B of comparative example 2 to 4 is less than 170 grams-micron/square metre-day (g-μm/m
2-day), and the aqueous vapor penetrance of the Thermocurable polyimide film 30B of comparative example 5 to 7 is more than or equal to 170g-μm/m
2-day; There is not delamination and albinism due to the aqueous vapor penetrance of the Thermocurable polyimide film 30B of comparative example 5 to 7 and be more than or equal to 170g-μm/m in the polyimides/metal composite laminated plates of display comparative example 5 to 7
2caused 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 the glass transition temperature of the Thermocurable polyimide film obtained after high temperature cyclization, thermal coefficient of expansion and aqueous vapor penetrance
Table 4 is denoted as glass transition temperature, thermal coefficient of expansion, the aqueous vapor penetrance of TPI acid predecessor via the thermoplastic polyimide film obtained after high temperature cyclization of TPI-1, TPI-2, TPI-3 and TPI-4.
The raw material of the stripping of the polyimides/metal composite laminated plates of table 5 comparative example 2 to 7, albinism and its thermoplastic polyimide film and Thermocurable polyimide film and thickness.
Compare comparative example 2 to 4 further again and comparative example 5 to 7 is known, the Thermocurable polyimide film 30B of comparative example 5 to 7 is respectively made by PI-4, PI-5 and PI-6, and the Thermocurable polyimide film 30B of comparative example 2 to 4 is respectively made by PI-1, PI-2 and PI-3; With the total mole number of the first reactive monomer and diamine monomer for benchmark, the first reactive monomer contained by PI-4, PI-5 and PI-6 is at least 2.7 molar percentages, and the first reactive monomer contained by PI-2 and PI-3 is lower than 2.7 molar percentages, PI-1 is not then containing the first reactive monomer.
As shown in table 6 and Fig. 7, delamination and albinism is there is not between the thermoplastic polyimide film 40C of the polyimides/metal composite laminated plates of comparative example 8 to 13 and Thermocurable polyimide film 30C, further cooperation with reference to table 4 and 5 known, because the aqueous vapor penetrance of the thermoplastic polyimide film 40C of comparative example 8 to 13 is greater than 170g-μm/m
2-day, makes the aqueous vapor between the thermoplastic polyimide film 40C of comparative example 8 to 13 and Thermocurable polyimide film 30C be discharged.
The raw material of the stripping of the polyimides/metal composite laminated plates of table 6 comparative example 8 to 13, albinism and its thermoplastic polyimide film and Thermocurable polyimide film and thickness.
Known by inference by above-mentioned, between the first Thermocurable polyimide film 30 of embodiment 1 to 9 and the first thermoplastic polyimide film 20; And, delamination and albinism is there is not between second thermoplastic polyimide film 40 and the first Thermocurable polyimide film 30, and between the first Thermocurable polyimide film 30 of the polyimides of comparative example 1/metal composite laminated plates and the first thermoplastic polyimide film 20; And, between second thermoplastic polyimide film 40 and the first Thermocurable polyimide film 30, delamination and albinism occur, this is because the first Thermocurable polyimide film 30 of embodiment 1 to 9 and the aqueous vapor penetrance of the second thermoplastic polyimide film 40 are more than or equal to 170g-μm/m
2-day, and embodiment 1 to 9 and the aqueous vapor penetrance of the second thermoplastic polyimide film 40 be greater than caused by the aqueous vapor penetrance of the first Thermocurable polyimide film 30.And above-mentioned know by inference by with diamine monomer and reactive monomer for benchmark, PI-4, PI-5 and PI-6 containing the first more than 3.39 molar percentages reactive monomers, can be more than or equal to 170g-μm/m by the aqueous vapor penetrance of the first Thermocurable polyimide film of embodiment 1 to 9 and the second thermoplastic polyimide film
2-day; And TPI-1, TPI-2, TPI-3 and the TPI-4 containing the second more than 35.89 molar percentages reactive monomers, the aqueous vapor penetrance of the second thermoplastic polyimide film of embodiment 1 to 9 can be more than or equal to 170g-μm/m
2-day.
As shown in table 1 and 2, the polyimide film/metal composite laminated plates of embodiment 1 to 9 was by the soldering resistance test of 300 DEG C/30 seconds, and the polyimide film/metal composite laminated plates of display embodiment 1 to 9 has good soldering resistance.
As shown in table 1 and 2, T.D. and M.D. of the dimensional stability (B) of the polyimide film/metal composite laminated plates of embodiment 1 to 9 levels off to 0, and T.D. and M.D. of the dimensional stability (C) of the polyimide film of embodiment 1 to 9/metal composite laminated plates levels off to 0, the polyimide film/metal composite laminated plates of display embodiment 1 to 9 has good dimensional stability.
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 greater than 0.8Kg/cm, and the polyimide film/metal composite laminated plates of display embodiment 1 to 9 has good peel strength.
In sum, by PI-4, PI-5 and the PI-6 containing the first more than 3.39 molar percentages reactive monomers and the use of TPI-1, TPI-2, TPI-3 and TPI-4 of the second reactive monomer containing more than 35.89 molar percentages, the first Thermocurable polyimide film of embodiment 1 to 9 and the second thermoplastic polyimide film have and are more than or equal to 170g-μm/m
2the aqueous vapor penetrance of-day, thus avoids the generation of delamination and albinism, and learns via test, and the polyimide film/metal composite laminated plates of embodiment 1 to 9 has good soldering resistance, dimensional stability and peel strength.
Claims (20)
1. polyimides/metal composite laminated plates, wherein comprises:
First metal film;
First thermoplastic polyimide film, its recline be overlapped in described first metal film a side on;
First Thermocurable polyimide film, it reclines and is overlapped on the side of described first thermoplastic polyimide film away from described first metal film, and the aqueous vapor penetrance of described first Thermocurable polyimide film be not less than 170 grams-micron/square metre-day; And,
Second thermoplastic polyimide film, it reclines and is overlapped on the side of described first Thermocurable polyimide film away from described first thermoplastic polyimide film, and the aqueous vapor penetrance of described second thermoplastic polyimide film is not less than the aqueous vapor penetrance of described first Thermocurable polyimide film.
2. polyimides/metal composite laminated plates as claimed in claim 1, wherein comprise the second metal film, described second metal film reclines and is overlapped on the side of described second thermoplastic polyimide film away from described first Thermocurable polyimide film.
3. polyimides/metal composite laminated plates as claimed in claim 2, wherein comprise the 3rd thermoplastic polyimide film, described second metal film reclines through described 3rd thermoplastic polyimide film and is overlapped on described second thermoplastic polyimide film.
4. polyimides/metal composite laminated plates as claimed in claim 3, wherein comprise the second Thermocurable polyimide film, described 3rd thermoplastic polyimide film reclines through described second Thermocurable polyimide film and is overlapped on described second thermoplastic polyimide film.
5. polyimides/metal composite laminated plates as claimed in claim 4, wherein comprise the 4th thermoplastic polyimide film, described second Thermocurable polyimide film reclines through described 4th thermoplastic polyimide film and is overlapped in described second thermoplastic polyimide film and connects.
6. the polyimides according to any one of claim 1 to 5/metal composite laminated plates, the aqueous vapor penetrance of wherein said second thermoplastic polyimide film be not less than 200 grams-micron/square metre-day.
7. the polyimides according to any one of claim 1 to 5/metal composite laminated plates, the aqueous vapor penetrance of wherein said first Thermocurable polyimide film be not less than 200 grams-micron/square metre-day.
8. the polyimides according to any one of claim 1 to 5/metal composite laminated plates, the overall aqueous vapor penetrance of wherein said first thermoplastic polyimide film, described first Thermocurable polyimide film and described second thermoplastic polyimide film be not less than 180 grams-micron/square metre-day between.
9. the polyimides according to any one of claim 1 to 5/metal composite laminated plates, the gross thickness of wherein said first thermoplastic polyimide film, described first Thermocurable polyimide film and described second thermoplastic polyimide film is between 9 microns to 25 microns.
10. a preparation method for polyimides/metal composite laminated plates, its step comprises:
By the first diamine monomer, first reactive monomer and the first dianhydride monomer are polymerized in the first solvent, to obtain Thermocurable polyimide predecessor, described first reactive monomer is selected from by 2, two (4-aminophenyl) propane of 2'-, 1, two (3-amino-benzene oxygen) benzene of 3-, 4, 4'-(1, 3-diisopropyl alkylbenzene) diphenylamines, 9, the group that two (4-aminophenyl) fluorenes of 9'-and polyoxypropylene ether diamine are formed, and with the total mole number of described first diamine monomer and described first reactive monomer for benchmark, the molal quantity of described first reactive monomer is between 3.00 to 7.00 molar percentages,
By the second diamine monomer, second reactive monomer and the second dianhydride monomer are polymerized in the second solvent, to obtain TPI predecessor, described second reactive monomer is selected from by 2, two (4-aminophenyl) propane of 2'-, 1, two (3-amino-benzene oxygen) benzene of 3-, 4, 4'-(1, 3-diisopropyl alkylbenzene) diphenylamines, 9, the group that two (4-aminophenyl) fluorenes of 9'-and polyoxypropylene ether diamine are formed, and with the total mole number of described second diamine monomer and described second reactive monomer for benchmark, the molal quantity of described second reactive monomer is between 35.00 to 65.00 molar percentages,
Be coated with described TPI predecessor on a side of the first Copper Foil, to form the first TPI precursor layer;
Be coated with described Thermocurable polyimide predecessor on the side of described first TPI precursor layer away from described first Copper Foil, with shaping first Thermocurable polyimide precursor layer;
Be coated with described TPI predecessor on the side of described first Thermocurable polyimide precursor layer away from described first TPI precursor layer, with shaping second TPI precursor layer; And,
Be the first thermoplastic polyimide film, the first Thermocurable polyimide film and the second thermoplastic polyimide film by described first TPI precursor layer, described first Thermocurable polyimide precursor layer and described second TPI precursor layer cyclisation, obtain described polyimides/metal composite laminated plates.
The preparation method of 11. polyimides/metal composite laminated plates as claimed in claim 10, wherein, be described first thermoplastic polyimide film, described first Thermocurable polyimide film and described second thermoplastic polyimide film by described first TPI precursor layer, described first Thermocurable polyimide precursor layer and described second TPI precursor layer cyclisation, the step obtaining described polyimides/metal composite laminated plates comprises further:
It is the step of described first thermoplastic polyimide film, described first Thermocurable polyimide film and the sub-thing film of described second thermoplasticity polyamides by described first TPI precursor layer, described first Thermocurable polyimide precursor layer and described second TPI precursor layer cyclisation; And,
Pressing second Copper Foil, on the side of described second thermoplastic polyimide film away from described first Thermocurable polyimide film, obtains the step of described polyimides/metal composite laminated plates.
The preparation method of 12. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, be described first thermoplastic polyimide film, described first Thermocurable polyimide film and described second thermoplastic polyimide film by described first TPI precursor layer, described first Thermocurable polyimide precursor layer and described second TPI precursor layer cyclisation, the step obtaining described polyimides/metal composite laminated plates comprises further:
80 DEG C to 150 DEG C desolventize temperature under, removing described first TPI precursor layer, described first Thermocurable polyimide precursor layer and the solvent contained by described second TPI precursor layer, obtaining the first TPI precursor layer through removing solvent, through removing the step of the first Thermocurable polyimide precursor layer of solvent and the second TPI precursor layer through removing solvent; And
Described the first TPI precursor layer through removing solvent, described the first Thermocurable polyimide precursor layer through removing solvent and described the second TPI precursor layer through removing solvent are sequentially heated to simultaneously the temperature of the temperature of 160 DEG C to 190 DEG C, the temperature of 190 DEG C to 300 DEG C and 300 DEG C to 350 DEG C, be described first thermoplastic polyimide film, described first Thermocurable polyimide film and described second thermoplastic polyimide film with cyclisation respectively, obtain the step of described polyimides/metal composite laminated plates.
The preparation method of 13. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, by described first diamine monomer, described first reactive monomer and described first dianhydride monomer are polymerized in described first solvent, and to obtain in the step of described Thermocurable polyimide predecessor, described first diamine monomer is selected from by 3,4'-diamino-diphenyl ether, 4,4'-diamino-diphenyl ether, p-phenylenediamine (PPD), m-phenylene diamine (MPD), 3,5-diaminobenzoic acid, two (4-aminophenyl) propane of 2,2'-, 4,4'-diaminodiphenyl-methane, 4,4'-diamino diphenyl sulfone, 3,3'-diamino diphenyl sulfone, 4,4'-diamino diphenyl sulfide, two (4-amino-benzene oxygen) benzene of 1,3-, two (3-amino-benzene oxygen) benzene of 1,3-, two (4-the amino-benzene oxygen)-biphenyl of Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene 4,4-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2'-, two [4-(the 3-amino-benzene oxygen benzene) base] propane of 2,2'-, 2,2'-dimethyl-4,4'-benzidine 3,3'-dimethyl-4,4'-benzidine, 3,3'-dialkyl-4,4'-benzidine, two (4-aminophenyl) fluorenes of 9,9'-, two (4-[3-amino-benzene oxygen] phenyl) sulfone of 2,2'-, 2,6-di-amino-pyrimidine, polypropylene ether diamines, 4,4'-(1,3-diisopropyl alkylbenzene) diphenylamines, 4,4'-(Isosorbide-5-Nitrae-diisopropyl alkylbenzene) diphenylamines, the group that bornylane diamines and combination thereof are formed.
The preparation method of 14. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, by described first diamine monomer, described first reactive monomer and described first dianhydride monomer are polymerized in described first solvent, to obtain in the step of described Thermocurable polyimide predecessor, described first dianhydride monomer is selected from by the equal tetracarboxylic dianhydride of benzene, 3, 3', 4, 4'-biphenyl tetracarboxylic dianhydride, 3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride, 4, 4'-oxygen two phthalic acid dianhydride, 3, 3', 4, 4'-diphenyl sulfone tetrabasic carboxylic acid two, 2, 2'-two (3, 4-dicarboxyphenyi) HFC-236fa, ethylene glycol-bis-trimellitic anhydride, 1, 3-dihydro-1, the sub-phenyl ester of 3-dioxy-5-isobenzofuran carboxylic acid, 1, 2, 3, 4-butane tetracarboxylic acid dianhydride, 1, 2, 3, the group that 4-pentamethylene tetracarboxylic dianhydride and combination thereof are formed.
The preparation method of 15. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, described first diamine monomer, described first reactive monomer and described first dianhydride monomer are polymerized in described first solvent, to obtain in the step of described Thermocurable polyimide predecessor, described first solvent is selected from by oxolane, N, the group that dinethylformamide, DMA, METHYLPYRROLIDONE, gamma-butyrolacton and combination thereof are formed.
The preparation method of 16. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, by described second diamine monomer, described second reactive monomer and described second dianhydride monomer are polymerized in described second solvent, and to obtain in the step of described TPI predecessor, described second diamine monomer is selected from by 3,4'-diamino-diphenyl ether, 4,4'-diamino-diphenyl ether, p-phenylenediamine (PPD), m-phenylene diamine (MPD), 3,5-diaminobenzoic acid, two (4-aminophenyl) propane of 2,2'-, 4,4'-diaminodiphenyl-methane, 4,4'-diamino diphenyl sulfone, 3,3'-diamino diphenyl sulfone, 4,4'-diamino diphenyl sulfide, two (4-amino-benzene oxygen) benzene of 1,3-, two (3-amino-benzene oxygen) benzene of 1,3-, two (4-the amino-benzene oxygen)-biphenyl of Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene 4,4-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2'-, two [4-(the 3-amino-benzene oxygen benzene) base] propane of 2,2'-, 2,2'-dimethyl-4,4'-benzidine 3,3'-dimethyl-4,4'-benzidine, 3,3'-dialkyl-4,4'-benzidine, two (4-aminophenyl) fluorenes of 9,9'-, two (4-[3-amino-benzene oxygen] phenyl) sulfone of 2,2'-, 2,6-di-amino-pyrimidine, polypropylene ether diamines, 4,4'-(1,3-diisopropyl alkylbenzene) diphenylamines, 4,4'-(Isosorbide-5-Nitrae-diisopropyl alkylbenzene) diphenylamines, the group that bornylane diamines and combination thereof are formed.
The preparation method of 17. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, by described second diamine monomer, described second reactive monomer and described second dianhydride monomer are polymerized in described second solvent, to obtain in the step of described Thermocurable polyimide predecessor, described second dianhydride monomer is selected from by the equal tetracarboxylic dianhydride of benzene, 3, 3', 4, 4'-biphenyl tetracarboxylic dianhydride, 3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride, 4, 4'-oxygen two phthalic acid dianhydride, 3, 3', 4, 4'-diphenyl sulfone tetrabasic carboxylic acid two, 2, 2'-two (3, 4-dicarboxyphenyi) HFC-236fa, ethylene glycol-bis-trimellitic anhydride, 1, 3-dihydro-1, the sub-phenyl ester of 3-dioxy-5-isobenzofuran carboxylic acid, 1, 2, 3, 4-butane tetracarboxylic acid dianhydride, 1, 2, 3, the group that 4-pentamethylene tetracarboxylic dianhydride and combination thereof are formed.
The preparation method of 18. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, described second diamine monomer, described second reactive monomer and described second dianhydride monomer are polymerized in described second solvent, to obtain in the step of described Thermocurable polyimide predecessor, described second solvent is selected from by oxolane, N, the group that dinethylformamide, DMA, METHYLPYRROLIDONE, gamma-butyrolacton and composition thereof are formed.
The preparation method of 19. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, described first diamine monomer, described first reactive monomer and described first dianhydride monomer are being polymerized, to obtain in the step of described Thermocurable polyimide predecessor, with the total mole number of described first diamine monomer and described first reactive monomer for benchmark, the molal quantity of described first reactive monomer is between 3.00 to 7.00 molar percentages.
The preparation method of 20. polyimides/metal composite laminated plates as described in claim 10 or 11, wherein, described second diamine monomer, described second reactive monomer and described second dianhydride monomer are being polymerized, to obtain in the step of described TPI predecessor, with the total mole number of described second diamine monomer and described second reactive monomer for benchmark, the molal quantity of described second reactive monomer is between 35.00 to 65.00 molar percentages.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410178745.7A CN105015099B (en) | 2014-04-30 | 2014-04-30 | Polyimides/metal composite laminated plates and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410178745.7A CN105015099B (en) | 2014-04-30 | 2014-04-30 | Polyimides/metal composite laminated plates and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105015099A true CN105015099A (en) | 2015-11-04 |
| CN105015099B CN105015099B (en) | 2017-06-06 |
Family
ID=54405558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410178745.7A Active CN105015099B (en) | 2014-04-30 | 2014-04-30 | Polyimides/metal composite laminated plates and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105015099B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021120191A1 (en) * | 2019-12-20 | 2021-06-24 | 瑞声声学科技(深圳)有限公司 | Polyimide composite metal plate |
| 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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200416242A (en) * | 2002-09-20 | 2004-09-01 | Du Pont | High modulus polyimide compositions useful as dielectric substrates for electronics applications, and methods relating thereto |
| US20070044910A1 (en) * | 2005-08-31 | 2007-03-01 | Thinflex Corporation | Polyimide based flexible copper clad laminates and method of producing the same |
| CN101353424A (en) * | 2008-05-21 | 2009-01-28 | 广东生益科技股份有限公司 | Thermoplastic polyimide resin containing active lateral group, flexible copper clad laminate manufactured with the same and manufacturing method thereof |
| CN101448879A (en) * | 2006-05-19 | 2009-06-03 | 宇部兴产株式会社 | Method for producing polyimide film and polyamic acid solution composition |
| CN101998761A (en) * | 2009-08-26 | 2011-03-30 | 比亚迪股份有限公司 | Metal lamination plate and preparation method thereof |
| CN102408564A (en) * | 2011-08-30 | 2012-04-11 | 广东生益科技股份有限公司 | Thermoplastic polyimide and preparation method of two-layer process adhesive-free double-side flexible copper clad plate using thermoplastic polyimide |
| CN102909934A (en) * | 2012-11-06 | 2013-02-06 | 江苏科技大学 | Manufacture method of flexible glue-free double-face copper clad |
| CN103660490A (en) * | 2013-11-25 | 2014-03-26 | 昆山永翔光电科技有限公司 | Manufacturing method for two-layer method produced double-side flexible copper-clad plate |
-
2014
- 2014-04-30 CN CN201410178745.7A patent/CN105015099B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200416242A (en) * | 2002-09-20 | 2004-09-01 | Du Pont | High modulus polyimide compositions useful as dielectric substrates for electronics applications, and methods relating thereto |
| US20070044910A1 (en) * | 2005-08-31 | 2007-03-01 | Thinflex Corporation | Polyimide based flexible copper clad laminates and method of producing the same |
| CN101448879A (en) * | 2006-05-19 | 2009-06-03 | 宇部兴产株式会社 | Method for producing polyimide film and polyamic acid solution composition |
| CN101353424A (en) * | 2008-05-21 | 2009-01-28 | 广东生益科技股份有限公司 | Thermoplastic polyimide resin containing active lateral group, flexible copper clad laminate manufactured with the same and manufacturing method thereof |
| CN101998761A (en) * | 2009-08-26 | 2011-03-30 | 比亚迪股份有限公司 | Metal lamination plate and preparation method thereof |
| CN102408564A (en) * | 2011-08-30 | 2012-04-11 | 广东生益科技股份有限公司 | Thermoplastic polyimide and preparation method of two-layer process adhesive-free double-side flexible copper clad plate using thermoplastic polyimide |
| CN102909934A (en) * | 2012-11-06 | 2013-02-06 | 江苏科技大学 | Manufacture method of flexible glue-free double-face copper clad |
| CN103660490A (en) * | 2013-11-25 | 2014-03-26 | 昆山永翔光电科技有限公司 | Manufacturing method for two-layer method produced double-side flexible copper-clad plate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021120191A1 (en) * | 2019-12-20 | 2021-06-24 | 瑞声声学科技(深圳)有限公司 | Polyimide composite metal plate |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105015099B (en) | 2017-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107325285B (en) | Polyimide, polyimide-based adhesive, adhesive material, adhesive layer, adhesive sheet, laminate, wiring board, and method for producing same | |
| TWI400268B (en) | Thermosetting resin composition and use thereof | |
| TWI572479B (en) | Metal laminate with polyimide resin and method for manufaturing thereof | |
| TWI814908B (en) | Metal-clad laminates and circuit boards | |
| TWI595024B (en) | Polyamic acid, copper clad laminate and circuit board | |
| CN112521603B (en) | Polyamic acid block copolymer, preparation method thereof, polyimide copper-clad plate and circuit board | |
| KR20110013461A (en) | Linear polyimide precursor, linear polyimide, thermally cured product of the linear polyimide, and method for producing the linear polyimide | |
| JP2020056011A (en) | Resin film, coverlay film, circuit board, copper foil with resin, metal-clad laminate, multilayer circuit board, polyimide and adhesive resin composition | |
| CN111132456A (en) | Metal-clad laminate, circuit board, multilayer circuit board, and method for manufacturing same | |
| CN105367794B (en) | Soluble thermoplastic polyimide composition and laminate made therefrom | |
| CN105015099A (en) | Polyimide/metal composite laminated plate and preparation method thereof | |
| JP2004315754A (en) | Thermosetting resin composition, and laminated body and circuit board using the same | |
| JP2943953B2 (en) | Heat resistant adhesive | |
| JP2952868B2 (en) | Heat resistant adhesive | |
| TWI764046B (en) | Polyamic acid block copolymer and preparation method thereof, polyimide coated copper plate and circuit board thereof | |
| US9694569B2 (en) | Polyimide metal laminated plate and method of making the same | |
| TWI516366B (en) | Polyimide / metal composite laminated board and its preparation method | |
| JP3356096B2 (en) | Polyimide siloxane used as an essential component of adhesives | |
| TWI388260B (en) | Single - sided soft copper foil laminated board and its manufacturing method | |
| CN107916090B (en) | Low-modulus high-bonding-capacity thermoplastic polyimide composition and application and preparation method thereof | |
| TW201720858A (en) | Polyimide polymer, polyimide film, and flexible copper-coated laminate | |
| JP2020117699A (en) | Polyimide | |
| JP7231931B2 (en) | polyimide film | |
| JP7231932B2 (en) | polyimide film | |
| JP6937509B2 (en) | Oligoaminomaleimide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |