CN102993748B - Polyimide film and method for preparing double-layer flexible copper-clad plate by utilizing same - Google Patents
Polyimide film and method for preparing double-layer flexible copper-clad plate by utilizing same Download PDFInfo
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Abstract
The invention relates to thermoplastic polyimide (TPI) film with low coefficient of thermal expansion, a preparation method of the TPI film, and a method for preparing a double-layer flexible copper-clad plate (2L-FCCL) by utilizing the TPI film. The preparation method of the TPI film comprises the following steps in sequence: polymerizing bi(4-aminobenzene)-4-(tribromomethyl) phenylphosphine and 3-phenyl-2, 6-bi(4-aminobenzene) pyridine on a certain mole ratio with relative diamine and dianhydride in form of solution, so as to obtain a polyamide acid copolymer; drying to remove the solvent; and carrying out thermal imidization to process the copolymer, thus obtaining the TPI film which is excellent in hot melting performance and dimensional stability. According to the method for preparing the double-layer flexible copper-clad plate by the TPI film, the TPI film is compounded with a thermoset polyimide film and a copper foil under a certain pressure and temperature, thus obtaining the double-layer flexible copper-clad plate which is excellent in comprehensive performances, such as stripping quality and dimensional stability.
Description
Technical field
The present invention relates to preparation and there is the polyimide material field of good hot melt processing characteristics and low thermal expansion coefficient thermoplastic, and utilize thermoplastic polyimide material to prepare the method for flexible polyimide copper-clad plate.
Technical background
Polyimide (PI) film is one of basic material that flexible copper-clad board industry is conventional, another two kind insulating substrate polyester films and the poly-naphthalene film conventional with respect to flexible copper-clad plate, it is high that Kapton has intensity, good toughness, the features such as resistance toheat is superior, particularly its superior for heat resistance, can tolerate 500 DEG C of high temperature at short notice, and can be below 300 DEG C life-time service.But in having premium properties, also there is the defect that is difficult to hot melt processing in polyimide.Thermoplastic polyimide (TPI) is a quasi-polyimide material that starts suitability for industrialized production the beginning of the sixties in last century, by introduce the monomer of flexible group or the non-coplanar structure of distortion in molecular structure, make gained polyimide material there is good melting behaviour, can adopt extrude, the plastics molding process method of the routine such as injection and mold pressing carries out machine-shaping (Terry L S, Fay C C.Working PolyimideFibers[P] .US Pat, 5840828,1998; Yamada H, Fukudome M, Egawa N, et al.Methodfor producing polyimide film[P] .US Pat, 6264866,2001; Shih S C, Lu C S, King J S.Thermoplastic polyimide composition[P] .US Pat, 7459518,2006).Simultaneously, the excellent specific property of TPI is also embodied in the aspects such as high-low temperature resistant, corrosion-resistant, mechanical property and self-lubricating property are outstanding, most typical example is the polyetherimide PEI being made by the introducing flexible group in polyimide (PI) main chain of GE company of the U.S. exploitation nineteen eighty-two, release again new PEI the end of the year 2006, comprising it U.S. Mt.Vernon's
series P EI resin, this improvement makes the thermotolerance temperature of PEI resin bring up to 300 DEG C of (Yang Shiyong, Gao Shengqiang from 230 DEG C, Hu Aijun, Deng. the progress [J] of high temperature resistant polyimide resin and matrix material thereof. aerospace material technique, 2000,30 (1): 1～6).Thermoset PI is chemically crosslinked, moulding again after solidifying, and TPI is the linear polymer of complete reaction, contains the part of imine group-CONCO-as polymer chain, there is no chemically crosslinked between processing period, can be by molding and reshaping again.
In the last few years, use the electronic product of flexible circuit board (FPC) to present high-density and microminiaturized trend, this has higher requirement to the flexible copper-clad plate as baseplate of flexible circuit board, also makes two sheets of flexible copper-clad plate (2L-FCCL) development of gum-free rapidly.Two sheets of flexible copper-clad plate is only made up of Kapton and Copper Foil, the problems such as not environmental protection, poor dimensional stability, thermotolerance that three layer flexible cover copper plates (3L-FCCL) use sizing agent to bring be relatively low are not only overcome, because thickness greatly reduces, make it better adapt to the developing direction of FPC simultaneously.Being widely used of 3L-FCCL at present, production technique is also comparatively ripe.2L-FCCL, because its base material PI is had higher requirement, nowadays also has certain achievement in research and industrial scale.Wherein more existing scale operation of American-European countries, Japan and TaiWan, China, China's Mainland only have at present small serial production and achievement in research few.The production technique of 2L-FCCL mainly contains three kinds at present: coating method (Casting), sputter electrochemical plating (Sputtering); laminating (Lamination) (Lee H K; Son S H; Koo SB.System and method for manufacturing flexible copper clad laminate film[P] .USPat; 7678242,2005; Tan M Y.Double sided flexible printed circuit board[P] .US Pat, 7545649,2006; Chen Y C, Lee H K.Flexible copper foil structure and fabricationmethod therefor[P] .US Pat, 7052781,2006).
The disclosed clear 61-275325 of Japan's approval in 1986 about the patent of two-layer FCCL the earliest, this patent relates to coating method and prepares 2L-FCCL, be coated on copper foil surface by polyimide resin (PI) multipolymer, then obtain two layers of polyimide flexible copper-clad plate through hot imidization.In the disclosed patent CN102492297A of China, also introduce the composition of a kind of coating method polyimide material used and prepared the method for single-sided flexible copper-clad plate, in patent ZL200920093960.7, describe a kind of baking oven of can serialization producing coating method 2L-FCCL, used this baking oven can realize coating method and produce the technique that 2L-FCCL is prepared in related continuous imidization.It is low that coating method is prepared 2L-FCCL facility investment, and production technique is relatively simple, and production cost is low, in the production of current 2L-FCCL, occupies very large proportion.But coating method is prepared the manufacture that the technique of 2L-FCCL is difficult to realize dual platen flexible copper-clad plate, the technique of laminating can head it off.Laminating is normally taking thermoset PI film as base material, at it one-sided or both sides compound on the glued membrane of thermoplastic polyimide (TPI), thereby then utilize High Temperature High Pressure that TPI and Copper Foil are pressed together and make single or double 2L-FCCL.Pixeo film (the wangkai that for example Japanese Zhong Yuan chemical industrial company develops, Gao Shengqiang, Zhan Maosheng, Deng. development of Thermoplastic Polyimide [J], polymer circular, 2005,6 (3): 25～32), it is divided into three kinds of product grades according to different combined temps, is respectively TP-D, TP-T and TP-E.In actual production application, the thermalexpansioncoefficientα of TPI film is to determine that can it enter the topmost technical indicator of flexible print circuit.Flexible copper-clad plate is composited by PI film and copper, therefore will make high-density circuit board, and the thermal expansivity of TPI film must be consistent with copper, and the α of known copper is 1.6 × 10 at present
-5～1.8 × 10
-5/ DEG C, and the α of most PI film is generally 4.0 × 10
-5/ DEG C left and right, therefore develops α 2.5 × 10
-5/ DEG C following PI film is the Expansion Ways of product applications, and this is also to realize directly laminating prerequisite.
Summary of the invention
The present invention is directed to laminating and prepare the demand of the required polyimide of two sheets of flexible copper-clad plate, provide one to there is good hot melt processing characteristics, have relatively low thermel expansion coefficient (to be less than 2.5 × 10 simultaneously
-5/ DEG C) thermoplastic polyimide (TPI) film, and utilize this material to prepare the method for two sheets of flexible copper-clad plate.
Technical scheme of the present invention is: the preparation method of thermoplastic polyimide (TPI) film of described low thermal coefficient of expansion is made up of following steps:
1) reactor band being refluxed is full of with nitrogen, then the diamine monomer preparing is added in this reactor, and at 45 DEG C, constant temperature stirs, be dissolved in organic solvent, after dissolving completely, temperature of reaction be down to 10 ~ 20 DEG C, divide subsequently 5 times, every minor tick adds dianhydride monomer for 10 ~ 20 minutes.After dianhydride monomer adds, 10 ~ 20 DEG C of isothermal reactions 6 ~ 18 hours, get final product to obtain polyamic acid copolymer solution.Wherein the preparation method of diamine monomer is: in non-protonic solvent, add two (4-amido benzene)-4-(trisbromomethyl) phenyl phosphine oxide and 3-phenyl-2 of certain mol proportion (4:1～1:2), 6-bis-(4-aminocarbonyl phenyl) pyridine, add again 4,4 '-methylene radical two (2-tertiary butyl aniline), Ursol D, 4,4 '-diaminodiphenylmethane, mphenylenediamine and 4, in 4 '-diaminodiphenyl oxide a kind or several; Dianhydride monomer is selected 3,3-diphenyl sulfide-4, and 4 ', 5,5 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4, in 4 '-diphenyl ether tetraformic dianhydride and pyromellitic acid anhydride a kind or several; Described organic solvent is selected DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), acetone, butanone, in N-Methyl pyrrolidone a kind or several.When synthetic, total mol ratio of dianhydride monomer and diamine monomer is controlled between 0.99 ~ 1.08.
2) this polyamic acid copolymer solution being adjusted to mass percentage concentration with organic solvent used in step 1 is 10 ~ 15%, then this polyamic acid copolymer solution is coated on sheet glass, control coating thickness is 0.012 ~ 0.019mm, the sheet glass of film is placed in to vacuum drying oven, following dry 10 hours at 100 DEG C, heat-treat according to following heating schedule subsequently: 180 DEG C 2 hours, 200 DEG C 2 hours, 280 DEG C of 250 DEG C and 2 hours 1 hour, obtain thermoplastic polyimide (TPI) film.
The present invention also comprises that one utilizes gained thermoplastic polyimide film to prepare the method for two sheets of flexible copper-clad plate (2L-FCCL), be specially: the TPI film of gained of the present invention is placed in to press, both sides respectively with thick Thermocurable polyimide (PI) film of 0.025 ~ 0.080mm and the thick Copper Foil of 0.018 ~ 0.100mm compound after, at 210 ~ 260 DEG C, under the condition of 2.0 ~ 3.0MPa, suppress 10min, obtain single-sided flexible copper-clad plate.Or, by fit the respectively TPI film of upper gained of the present invention of thick Thermocurable polyimide (PI) the film both sides of 0.025 ~ 0.080mm, be placed in press, then the thick Copper Foil of 0.018 ~ 0.100mm on compound again in both sides, at 210 ~ 260 DEG C, under the condition of 2.0 ~ 3.0MPa, suppress 10min, obtain double-faced flexible copper-clad plate; Wherein Thermocurable polyimide (PI) film is synthesized and is made by pyromellitic acid anhydride and diaminodiphenyl oxide.
The present invention uses Q2000 differential scanning calorimeter and Diamond static heat mechanical analyzer (TMA) to measure second-order transition temperature and the thermal expansivity of thermoplastic polyimide film.Wherein, Q2000 differential scanning calorimeter is purchased from TA company of the U.S., and Diamond static heat mechanical analyzer (TMA) is purchased from PerkinElmer company of the U.S..
Compared with prior art, its remarkable advantage is in the present invention: thermoplastic polyimide material provided by the invention has lower thermal expansivity (to be less than 2.5 × 10
-5/ DEG C), very close to the thermal expansivity (1.6 × 10 of copper
-5～1.8 × 10
-5/ DEG C), the two sheets of flexible copper-clad plate of preparing by it has good dimensional stability and other over-all propertieies.
Further illustrate the present invention below by embodiment.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment mono-:
The reactor that band is refluxed is full of nitrogen, add 3-phenyl-2 of 0.33mol, 6-bis-(4-aminocarbonyl phenyl) pyridine, two (4-amido benzene)-4-(trisbromomethyl) phenyl phosphine oxide of 0.19mol, 4 of 0.48mol, 4 '-methylene radical two (2-tertiary butyl aniline), temperature of reaction is risen to 45 DEG C, then constant temperature stirs 30min, all diamine monomers are dissolved in N-Methyl pyrrolidone, after dissolving completely, temperature of reaction is down to 19 DEG C, divide subsequently 5 times, every minor tick 10min adds 3 of 0.70mol, 3-diphenyl sulfide-4, 4 ', 5, the pyromellitic acid anhydride of 5 '-bibenzene tetracarboxylic dianhydride and 0.33mol.After dianhydride monomer adds, isothermal reaction 6 hours, obtains polyamic acid copolymer solution.This polyamic acid copolymer solution is adjusted to 13% with N-Methyl pyrrolidone, then solution is coated on sheet glass, control coating thickness at 0.017mm, by the sheet glass of film in vacuum drying oven, at 100 DEG C dry 10 hours, heat-treat according to following heating schedule subsequently: 180 DEG C 2 hours, 200 DEG C 2 hours, 250 DEG C of 2 hours and 280 DEG C 1 hour.Obtain thermoplastic polyimide (TPI) film.
The TPI film of this routine gained is placed in to press, both sides respectively with thick Thermocurable polyimide (PI) film of 0.025mm and the thick Copper Foil of 0.035mm compound after, under 210 ~ 260 DEG C, the condition of 2.0 ~ 3.0MPa, suppress 10min, obtain single-sided flexible copper-clad plate.
Embodiment bis-:
The reactor that band is refluxed is full of after nitrogen, add 3-phenyl-2 of 0.47mol, 6-bis-(4-aminocarbonyl phenyl) pyridine, two (4-amido benzene)-4-(trisbromomethyl) phenyl phosphine oxide of 0.19mol, 4 of 0.21mol, 4 of 4 '-methylene radical two (2-tertiary butyl aniline) and 0.13mol, 4 '-diaminodiphenyl oxide, temperature of reaction is risen to 45 DEG C, then constant temperature stirs 30min, make all diamine monomers be dissolved in N, in N-N,N-DIMETHYLACETAMIDE, after dissolving completely, temperature of reaction is down to 20 DEG C, divide subsequently 5 times, every minor tick 12min adds 3 of 0.70mol, 3-diphenyl sulfide-4, 4 ', 5, the pyromellitic acid anhydride of 5 '-bibenzene tetracarboxylic dianhydride and 0.33mol.After dianhydride monomer adds, isothermal reaction 6 hours, obtains polyamic acid copolymer solution.By the solid content N of this polyamic acid copolymer solution, N-N,N-DIMETHYLACETAMIDE is adjusted to 10%, then solution is coated on sheet glass, control coating thickness at 0.014mm, by the sheet glass of film in vacuum drying oven, at 100 DEG C dry 10 hours, heat-treat according to following heating schedule subsequently: 180 DEG C 2 hours, 200 DEG C 2 hours, 250 DEG C of 2 hours and 280 DEG C 1 hour.Obtain thermoplastic polyimide (TPI) film.
The thermoplastic polyimide film that on being fitted respectively in thick Thermocurable polyimide (PI) the film both sides of 0.040mm, this example obtains, be placed in press, then the thick Copper Foil of 0.018mm on compound again in both sides, under 210 ~ 260 DEG C, the condition of 2.0 ~ 3.0MPa, suppress 10min, obtain double-faced flexible copper-clad plate.
Embodiment tri-:
The reactor that band is refluxed is full of nitrogen, add 3-phenyl-2 of 0.29mol, 6-bis-(4-aminocarbonyl phenyl) pyridine, two (4-amido benzene)-4-(trisbromomethyl) phenyl phosphine oxide of 0.42mol, 4 of 0.29mol, 4 '-methylene radical two (2-tertiary butyl aniline), temperature of reaction is risen to 45 DEG C, then constant temperature stirs 30min, all diamine monomers are dissolved in N-Methyl pyrrolidone, after dissolving completely, temperature of reaction is down to 10 DEG C, divide subsequently 5 times, every minor tick 20min adds 3 of 0.23mol, 3-diphenyl sulfide-4, 4 ', 5, 5 '-bibenzene tetracarboxylic dianhydride, 3 of the pyromellitic acid anhydride of 0.33mol and 0.49mol, 3 ', 4, 4 '-diphenyl ether tetraformic dianhydride.After dianhydride monomer adds, isothermal reaction 12 hours, obtains polyamic acid copolymer solution.The solid content of this polyamic acid copolymer solution is adjusted to 13% with N-Methyl pyrrolidone, then solution is coated on sheet glass, control coating thickness at 0.012mm, by the sheet glass of film in vacuum drying oven, at 100 DEG C dry 10 hours, heat-treat according to following heating schedule subsequently: 180 DEG C 2 hours, 200 DEG C 2 hours, 250 DEG C of 2 hours and 280 DEG C 1 hour.Obtain thermoplastic polyimide (TPI) film.
The TPI film of this routine gained is placed in to press, both sides respectively with thick Thermocurable polyimide (PI) film of 0.080mm and the thick Copper Foil of 0.100mm compound after, under 210 ~ 260 DEG C, the condition of 2.0 ~ 3.0MPa, suppress 10min, obtain single-sided flexible copper-clad plate.
Embodiment tetra-:
The reactor that band is refluxed is full of after nitrogen, add 3-phenyl-2 of 0.45mol, 6-bis-(4-aminocarbonyl phenyl) pyridine, two (4-amido benzene)-4-(trisbromomethyl) phenyl phosphine oxide of 0.32mol, 4 of the Ursol D of 0.11mol and 0.12mol, 4 '-diaminodiphenyl oxide, temperature of reaction is risen to 45 DEG C, then constant temperature stirs 30min, make all diamine monomers be dissolved in N, in N-N,N-DIMETHYLACETAMIDE, after dissolving completely, temperature of reaction is down to 19 DEG C, divide subsequently 5 times, every minor tick 12min adds 3 of 0.50mol, 3-diphenyl sulfide-4, 4 ', 5, the pyromellitic acid anhydride of 5 '-bibenzene tetracarboxylic dianhydride and 0.50mol.After dianhydride monomer adds, isothermal reaction 10 hours, obtains polyamic acid copolymer solution.By the solid content N of this polyamic acid copolymer solution, N-N,N-DIMETHYLACETAMIDE is adjusted to 15%, then solution is coated on sheet glass, control coating thickness at 0.015mm, by the sheet glass of film in vacuum drying oven, at 100 DEG C dry 10 hours, heat-treat according to following heating schedule subsequently: 180 DEG C 2 hours, 200 DEG C 2 hours, 280 DEG C of 250 DEG C and 2 hours 1 hour.Obtain thermoplastic polyimide (TPI) film.
The thermoplastic polyimide film that on being fitted respectively in thick Thermocurable polyimide (PI) the film both sides of 0.040mm, this example obtains, be placed in press, the thick Copper Foil of 0.035mm on compound again in both sides, under 210 ~ 260 DEG C, the condition of 2.0 ~ 3.0MPa, suppress 10min, obtain double-faced flexible copper-clad plate.
Embodiment five:
The reactor that band is refluxed is full of nitrogen, add 3-phenyl-2 of 0.60mol, 6-bis-(4-aminocarbonyl phenyl) pyridine, two (4-amido benzene)-4-(trisbromomethyl) phenyl phosphine oxide of 0.12mol, the Ursol D of 0.28mol, temperature of reaction is risen to 45 DEG C, then constant temperature stirs 30min, and all diamine monomers are dissolved in N-Methyl pyrrolidone, after dissolving completely, temperature of reaction is down to 19 DEG C, divide subsequently 5 times, every minor tick 12min adds 3,3 ' of the pyromellitic acid anhydride of 0.60mol and 0.47mol, 4,4 '-diphenyl ether tetraformic dianhydride.After dianhydride monomer adds, isothermal reaction 18 hours, obtains polyamic acid copolymer solution.The solid content of this polyamic acid copolymer solution is adjusted to 13% with N-Methyl pyrrolidone, then solution is coated on sheet glass, control coating thickness at 0.016mm, by the sheet glass of film in vacuum drying oven, at 100 DEG C dry 10 hours, heat-treat according to following heating schedule subsequently: 180 DEG C 2 hours, 200 DEG C 2 hours, 250 DEG C of 2 hours and 280 DEG C 1 hour.Obtain thermoplastic polyimide (TPI) film.
The thermoplastic polyimide film that on being fitted respectively in thick Thermocurable polyimide (PI) the film both sides of 0.040mm, this example obtains, be placed in press, the thick Copper Foil of 0.035mm on compound again in both sides, under 210 ~ 260 DEG C, the condition of 2.0 ~ 3.0MPa, suppress 10min, obtain double-faced flexible copper-clad plate.
Embodiment six:
The reactor that band is refluxed is full of after nitrogen, add 3-phenyl-2 of 0.40mol, 6-bis-(4-aminocarbonyl phenyl) pyridine, 4 of two (4-amido benzene)-4-(trisbromomethyl) phenyl phosphine oxides of 0.20mol and 0.40mol, 4 '-diaminodiphenyl oxide, temperature of reaction is risen to 45 DEG C, then constant temperature stirs 30min, make all diamine monomers be dissolved in N, in N-N,N-DIMETHYLACETAMIDE, after dissolving completely, temperature of reaction is down to 19 DEG C, divide subsequently 5 times, every minor tick 12min adds 3 of 0.70mol, 3-diphenyl sulfide-4, 4 ', 5, the pyromellitic acid anhydride of 5 '-bibenzene tetracarboxylic dianhydride and 0.30mol.After dianhydride monomer adds, isothermal reaction 9 hours, obtains polyamic acid copolymer solution.By the solid content N of this polyamic acid copolymer solution, N-N,N-DIMETHYLACETAMIDE is adjusted to 13%, then solution is coated on sheet glass, control coating thickness at 0.019mm, by the sheet glass of film in vacuum drying oven, at 100 DEG C dry 10 hours, heat-treat according to following heating schedule subsequently: 180 DEG C 2 hours, 200 DEG C 2 hours, 250 DEG C of 2 hours and 280 DEG C 1 hour.Obtain thermoplastic polyimide (TPI) film.
The thermoplastic polyimide film that on being fitted respectively in thick Thermocurable polyimide (PI) the film both sides of 0.040mm, this example obtains, be placed in press, the thick Copper Foil of 0.035mm on compound again in both sides, under 210 ~ 260 DEG C, the condition of 2.0 ~ 3.0MPa, suppress 10min, obtain double-faced flexible copper-clad plate.
Embodiment seven:
The reactor that band is refluxed is full of after nitrogen, add 3-phenyl-2 of 0.60mol, 6-bis-(4-aminocarbonyl phenyl) pyridine, 4 of two (4-amido benzene)-4-(trisbromomethyl) phenyl phosphine oxides of 0.30mol and 0.10mol, 4 '-Ursol D, temperature of reaction is risen to 45 DEG C, then constant temperature stirs 30min, make all diamine monomers be dissolved in N, in N-N,N-DIMETHYLACETAMIDE, after dissolving completely, temperature of reaction is down to 19 DEG C, divide subsequently 5 times, every minor tick 12min adds the pyromellitic acid anhydride of 1.02mol.After dianhydride monomer adds, isothermal reaction 6 hours, obtains polyamic acid copolymer solution.By the solid content N of this polyamic acid copolymer solution, N-N,N-DIMETHYLACETAMIDE is adjusted to 13%, then solution is coated on sheet glass, control coating thickness at 0.015mm, by the sheet glass of film in vacuum drying oven, at 100 DEG C dry 10 hours, heat-treat according to following heating schedule subsequently: 180 DEG C 2 hours, 200 DEG C 2 hours, 250 DEG C of 2 hours and 280 DEG C 1 hour.Obtain thermoplastic polyimide (TPI) film.
The thermoplastic polyimide film that on being fitted respectively in thick Thermocurable polyimide (PI) the film both sides of 0.040mm, this example obtains, be placed in press, the thick Copper Foil of 0.035mm on compound again in both sides, under 210 ~ 260 DEG C, the condition of 2.0 ~ 3.0MPa, suppress 10min, obtain double-faced flexible copper-clad plate.
The TPI film obtaining in above-described embodiment is carried out to second-order transition temperature test and thermal expansivity test, and result is as shown in table 1, and gained 2L-FCCL carries out copper-clad plate performance test, and result is as shown in table 2.Wherein to described 2L-FCCL copper-clad plate performance test methods: stripping strength is according under method B(normality in IPC-TM-650-2.4.8) and method D(immersed solder after) test; Resistance to immersed solder temperature is tested according to IPC-TM-650-2.4.13 method; Water absorbability is tested according to IPC-TM-650-2.6.2 method; Folding resistance is tested according to JIS-C-6471 method; Dimensional stability is tested according to IPC-TM-650-2.4.4 method; Flame retardant resistance is tested according to JPCA-BM03-2003 method.
Second-order transition temperature and the thermal expansivity of the different embodiment gained of table 1 TPI film
| Embodiment | Second-order transition temperature (DEG C) | Thermal expansivity (10 -5/℃） |
| One | 221 | 2.4 |
| Two | 201 | 2.5 |
| Three | 211 | 2.1 |
| Four | 213 | 2.3 |
| Five | 209 | 2.1 |
| Six | 213 | 2.3 |
| Seven | 227 | 2.0 |
The performance of the each embodiment gained of table 2 two sheets of flexible copper-clad plate
Claims (8)
1. the thermoplastic polyimide TPI film of a low thermal coefficient of expansion, it is characterized in that, obtain polyamic acid copolymer solution by diamine monomer and dianhydride monomer by solution polymerization process, again by this polyamic acid copolymer solution coat on sheet glass, obtain low thermal expansion coefficient thermoplastic polyimide TPI film after dry; Wherein diamine monomer is two (4-amino-benzene)-4-(trisbromomethyl) phenyl phosphine oxide or 3-phenyl-2,6-bis-(4-aminophenyl) pyridine, with a kind or several combining in following diamines: 4,4 '-methylene radical two (2-tertiary butyl aniline), Ursol D, 4,4 '-diaminodiphenylmethane, mphenylenediamine and 4,4 '-diaminodiphenyl oxide; Dianhydride monomer is 3,3-diphenyl sulfide-4,4 ', 5, and 5 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4, in 4 '-diphenyl ether tetraformic dianhydride and pyromellitic acid anhydride a kind or several.
2. the thermoplastic polyimide TPI film of low thermal coefficient of expansion according to claim 1, it is characterized in that, two (4-amino-benzene)-4-(trisbromomethyl) phenyl phosphine oxide and 3-phenyl-2, the mol ratio of 6-bis-(4-aminophenyl) pyridine is 4:1～1:2.
3. the thermoplastic polyimide TPI film of low thermal coefficient of expansion according to claim 1, is characterized in that, total mol ratio of dianhydride monomer and diamine monomer is controlled between 0.99 ~ 1.08.
4. a preparation method for the thermoplastic polyimide TPI film of low thermal coefficient of expansion, is characterized in that, is made up of following steps:
1) nitrogen is full of to the reactor that band refluxes, then the diamine monomer described in claim 1 is added in this reactor, at 45 DEG C, constant temperature stirs, be dissolved in organic solvent, after dissolving completely, temperature of reaction be down to 10 ~ 20 DEG C, divide subsequently 5 times, every minor tick 10 ~ 20min adds the dianhydride monomer described in claim 1, and after dianhydride monomer adds, isothermal reaction 6 ~ 18 hours, obtains polyamic acid copolymer solution;
2) this polyamic acid copolymer solution is adjusted to mass percentage concentration 10 ~ 15% with step 1 organic solvent used, then this polyamic acid copolymer solution is coated on sheet glass, coating thickness is controlled at 0.012 ~ 0.019 mm, by the sheet glass of film in vacuum drying oven, 100 DEG C following dry 10 hours, heat-treat according to following heating schedule subsequently: 180 DEG C 2 hours, 200 DEG C 2 hours, 250 DEG C 2 hours 280 DEG C 1 hour, get final product to obtain thermoplastic polyimide TPI film.
5. the preparation method of the thermoplastic polyimide TPI film of low thermal coefficient of expansion according to claim 4, is characterized in that, described organic solvent is chosen DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), acetone, butanone, in N-Methyl pyrrolidone a kind or several.
6. one kind is utilized the method for the thermoplastic polyimide TPI film preparation two sheets of flexible copper-clad plate of the low thermal coefficient of expansion described in claim 1, it is characterized in that, the thermoplastic polyimide film of described low thermal coefficient of expansion is placed in to press, 10 min are suppressed with the thick Thermocurable polyimide PI film of 0.025 ~ 0.080 mm and the thick Copper Foil of 0.018 ~ 0.100 mm after compound respectively in both sides under 210 ~ 260 DEG C, the condition of 2.0 ~ 3.0 MPa, obtain single-sided flexible copper-clad plate; Or, fit respectively the thick Thermocurable polyimide PI film both sides of 0.025 ~ 0.080 mm thermoplastic polyimide film of upper low thermal coefficient of expansion, be placed in press, then the thick Copper Foil of 0.018 ~ 0.100 mm on compound again in both sides, under 210 ~ 260 DEG C, the condition of 2.0 ~ 3.0 MPa, suppress 10 min, obtain double-faced flexible copper-clad plate.
7. the method for preparing two sheets of flexible copper-clad plate according to claim 6, is characterized in that, described Thermocurable polyimide PI is synthetic by pyromellitic acid anhydride and diaminodiphenyl oxide.
8. the method for preparing two sheets of flexible copper-clad plate according to claim 6, is characterized in that, the preparation method of the thermoplastic polyimide film of described low thermal coefficient of expansion comprises:
1) nitrogen is full of to the reactor that band refluxes, then diamine monomer is added in this reactor, at 45 DEG C, constant temperature stirs, be dissolved in organic solvent, after dissolving completely, temperature of reaction be down to 10 ~ 20 DEG C, divide subsequently 5 times, every minor tick 10 ~ 20min adds dianhydride monomer, and after dianhydride monomer adds, isothermal reaction 6 ~ 18 hours, obtains polyamic acid copolymer solution; Wherein said diamine monomer is two (4-amino-benzene)-4-(trisbromomethyl) phenyl phosphine oxide and 3-phenyl-2 of mol ratio 4:1～1:2,6-bis-(4-aminophenyl) pyridine, add again a kind or several combining in following diamines: 4,4 '-methylene radical two (2-tertiary butyl aniline), Ursol D, 4,4 '-diaminodiphenylmethane, mphenylenediamine and 4,4 '-diaminodiphenyl oxide; Described dianhydride monomer is 3,3-diphenyl sulfide-4,4 ', 5, and 5 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4, in 4 '-diphenyl ether tetraformic dianhydride and pyromellitic acid anhydride a kind or several; Described organic solvent is chosen DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), acetone, butanone, in N-Methyl pyrrolidone a kind or several; Total mol ratio of dianhydride monomer and diamine monomer is controlled between 0.99 ~ 1.08;
2) this polyamic acid copolymer solution being adjusted to mass percentage concentration with step 1 organic solvent used is 10 ~ 15%, then this polyamic acid copolymer solution is coated on sheet glass, coating thickness is controlled at 0.012 ~ 0.019 mm, by the sheet glass of film in vacuum drying oven, 100 DEG C following dry 10 hours, heat-treat according to following heating schedule subsequently: 180 DEG C 2 hours, 200 DEG C 2 hours, 250 DEG C 2 hours 280 DEG C 1 hour, get final product to obtain thermoplastic polyimide TPI film.
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