CN102848643B - Two layers of method single-face flexibility copper-clad board and preparation method thereof - Google Patents
Two layers of method single-face flexibility copper-clad board and preparation method thereof Download PDFInfo
- Publication number
- CN102848643B CN102848643B CN201210335509.2A CN201210335509A CN102848643B CN 102848643 B CN102848643 B CN 102848643B CN 201210335509 A CN201210335509 A CN 201210335509A CN 102848643 B CN102848643 B CN 102848643B
- Authority
- CN
- China
- Prior art keywords
- phenylacetylene
- side base
- polyamic acid
- layers
- copper
- 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.)
- Active
Links
Landscapes
- Laminated Bodies (AREA)
Abstract
The invention provides a kind of two layers of method single-face flexibility copper-clad board and preparation method thereof, these two layers of method single-face flexibility copper-clad boards comprise: Copper Foil and the crosslinked polyimide resin bed be located on Copper Foil, described crosslinked polyimide resin bed is by after the polyamic acid resin imidization with phenylacetylene side base, again through Overheating Treatment, make to impel the phenylacetylene side base of polyimide resin to occur crosslinked.The present invention's two layers of method single-face flexibility copper-clad board, its insulating barrier is made up of crosslinked polyimide resin, while the main chain of this crosslinked polyimide resin has certain rigidity, there is certain pliability, and crosslink density can be controlled easily, there is outstanding pliability and resistance to deflection; Low thermal expansion coefficient polyimide with non-crosslinked type is compared, and the insulating barrier of two layers of method single-face flexibility copper-clad board of the present invention is owing to having the slight degree of cross linking, so it has lower water absorption rate, higher dimensional stability and better resistance to dip solderability.
Description
Technical field
The present invention relates to printed circuit board production field, particularly relate to a kind of two layers of method single-face flexibility copper-clad board and preparation method thereof.
Background technology
Flexible printed-circuit board has been widely used in the consumption electronic products such as notebook computer, mobile phone, personal digital assistant and digital camera, because electron trade technical requirement improves constantly, consumption electronic products move towards compact just fast, day by day require that corresponding flexibility coat copper plate is lighter and thinner and have high-fire resistance and high reliability.Two-layer method flexibility coat copper plate obtains in recent years owing to adopting all very excellent polyimide resin of mechanical property, electrical property and heat resistance and develops fast.
Existing two layers of many employing of method single-face flexibility copper-clad board are coated with polyimide resin on Copper Foil, and then baking-curing obtains.The polyimide resin being applied to glue-free single sided board generally adopts the thermoset polyimide resin of low thermal coefficient of expansion.TPI generally shall not be applied in the manufacture of two layers of method single-face flexibility copper-clad board, because its thermal coefficient of expansion is much larger than Copper Foil, the dimensional stability of sheet material can be caused poor.And the polyimides that span carrys out anhydride group can not be applied in two layers of method single-face flexibility copper-clad board, because its fragility is excessive, pliability and the flexibility requirement of flex plate cannot be met.
Summary of the invention
The object of the present invention is to provide a kind of two layers of method single-face flexibility copper-clad board, its insulating barrier is made up of crosslinked polyimide resin, there is good pliability and resistance to deflection, and, there is lower water absorption rate, higher dimensional stability and better resistance to dip solderability.
Another object of the present invention is to the preparation method that a kind of above-mentioned two layers of method single-face flexibility copper-clad board are provided, its two layers of method single-face flexibility copper-clad boards made have good pliability and resistance to deflection, and, there is lower water absorption rate, higher dimensional stability and better resistance to dip solderability.
For achieving the above object, the invention provides a kind of two layers of method single-face flexibility copper-clad board, comprise: Copper Foil and the crosslinked polyimide resin bed be located on Copper Foil, described crosslinked polyimide resin bed is by after the polyamic acid resin imidization with phenylacetylene side base, again through Overheating Treatment, make to impel the phenylacetylene side base of polyimide resin to occur crosslinked.
The described synthon with the polyamic acid resin of phenylacetylene side base comprises the aromatic diamine monomers with phenylacetylene side base, described in there is phenylacetylene side base aromatic diamine monomers be the mixture of one or more in following monomer structure:
Described in the described molecular weight content with the phenylacetylene side base of the polyamic acid resin of phenylacetylene side base is less than, there is 20% of the number-average molecular weight of the polyamic acid resin of phenylacetylene side base.
The described molecular weight content with the phenylacetylene side base of the polyamic acid resin of phenylacetylene side base for described in there is the 5-15% of the number-average molecular weight of the polyamic acid resin of phenylacetylene side base.
The described temperature with the polyamic acid resin imidization of phenylacetylene side base is 330-350 DEG C.
The described temperature with the polyamic acid resin imidization after-baking of phenylacetylene side base is more than or equal to 370 DEG C.
Described crosslinked polyimide resin layer thickness is 10-100 μm.
Described Copper Foil is electrolytic copper foil, and its thickness is 9-70 μm.
The present invention also provides a kind of preparation method of above-mentioned two layers of method single-face flexibility copper-clad board, comprises the steps:
Step 1, synthesis have the polyamic acid resin of phenylacetylene side base;
Step 2, provide Copper Foil, and at one of this Copper Foil, there is described in coating the polyamic acid resin of phenylacetylene side base on the surface;
Step 3, the Copper Foil being coated with the polyamic acid resin with phenylacetylene side base is sent into high temperature oven at the temperature of 330-350 DEG C, carry out imidization obtain single-sided copper foil covered board;
Step 4, the single-sided copper foil covered board after this complete imidization to be heat-treated being more than or equal at the temperature of 370 DEG C, obtained two layers of method single-face flexibility copper-clad board.
Beneficial effect of the present invention: the insulating barrier of the present invention's two layers of method single-face flexibility copper-clad board is made up of crosslinked polyimide resin, while the main chain of this crosslinked polyimide resin has certain rigidity, there is certain pliability, and crosslink density can be controlled easily, there is outstanding pliability and resistance to deflection; Low thermal expansion coefficient polyimide with non-crosslinked type is compared, and the insulating barrier of two layers of method single-face flexibility copper-clad board of the present invention is owing to having the slight degree of cross linking, so it has lower water absorption rate, higher dimensional stability and better resistance to dip solderability; The preparation method technique of the present invention's two layers of method single-face flexibility copper-clad board is simple, production efficiency is high, and cost is low, and its two layers of method single-face flexibility copper-clad boards made have good pliability and resistance to deflection, and, there is lower water absorption rate, higher dimensional stability and better resistance to dip solderability.
Detailed description of the invention
For further setting forth the technological means and effect thereof that the present invention takes, be described in detail below in conjunction with the preferred embodiments of the present invention.
The invention provides a kind of two layers of method single-face flexibility copper-clad board, comprising: Copper Foil and the crosslinked polyimide resin bed be located on Copper Foil.
Described crosslinked polyimide resin bed is by the polyamic acid resin with phenylacetylene side base, the polyimide resin that imidization obtains having phenylacetylene side base is carried out at 330 DEG C about-350 DEG C, heat-treat at higher than the temperature of 370 DEG C again, impel the phenylacetylene side base of polyimide resin occur crosslinked and make.Anhydride group polyimides is carried out relative to the span of the cross-linking type applied in prior art, the main chain of crosslinked polyimide of the present invention has certain rigidity and has certain pliability, and crosslink density can be controlled easily, there is pliability and resistance to deflection is still outstanding.Low thermal expansion coefficient polyimide with non-crosslinked type is compared, the insulating barrier of two layers of method single-face flexibility copper-clad board of the present invention owing to having the slight degree of cross linking, so have lower water absorption rate, higher dimensional stability and better resistance to dip solderability.
The described synthon with the polyamic acid resin of phenylacetylene side base comprises the aromatic diamine monomers with phenylacetylene side base, described in there is phenylacetylene side base aromatic diamine monomers be the mixture of one or more in following monomer structure:
In addition, the polyimide resin containing phenylacetylene base has obtained extensive investigation and application in Aero-Space industry, has many patents or open source literature to discuss its mechanism, application etc. both at home and abroad.Oldly an open source literature [the synthesis and characteries research of 4-phenylacetylene base aniline capped polyimides resin waiting people is built liter as domestic, macromolecule journal, 2007, (6): 519-523], discuss the synthesis containing alkynyl polyimide oligomer, the principle such as powder preparation and high-temperature cross-linking, step and performance, paper [the Highthermalstablethermoplastic-thermosettingpolyimidefil mbyuseofasymmetricdianhydride (a-BPDA) of the people such as external TakeshiSasaki, Polymer, vol.46:6968-6975] then discuss a kind of HMW containing phenylacetylene side base polyimides, and illustrate its synthesis, preparation and crosslinked situation.Especially noticeable document disclosed in these all thinks that crosslinking temperature must greater than or equal to 370 DEG C, and phenylacetylene base just can fully react, the initial crosslinking temperature of phenylacetylene base then a little less than its crosslinking temperature, and higher than 350 DEG C.
Polyimide resin of the present invention selects the polyimide resin containing phenylacetylene side base.The polyimide resin of phenylacetylene base end-blocking generally can not get larger molecular weight, general generation be all oligomer, the apparent viscosity of presoma is very low, and mobility is too strong, being not easy when being coated with to control coating thickness and precision, being not suitable for the making being applied to two-layer method flexibility coat copper plate; And phenylacetylene base is positioned at after on side chain, do not affect the condensation reaction on polyimides main chain, therefore the presoma viscosity generated is higher, is suitable for coating, is applicable to the making being applied to two-layer method flexibility coat copper plate.Polyimide resin of the present invention selects side base to be the polyimide resin of phenylacetylene base.The present invention adopts the commercialization of phenylacetylene side monomers, can commercially buy on a large scale, and the main chain of such monomer is divided into two kinds: a kind of to be main chain be rigidity containing phenylacetylene side monomers, it is a kind of that to be main chain be is flexible containing phenylacetylene side monomers.Main chain be rigidity anamorphic zone can be cross-linked the thermosetting polyamide acid resin of side base containing after phenylacetylene side monomers and corresponding anhydride reaction; Main chain is flexible anamorphic zone can be cross-linked the polyamide thermoplastic acid resin of side base containing after phenylacetylene side monomers and corresponding anhydride reaction.The latter still has thermoplasticity at not higher than the temperature of 370 DEG C, can carry out melting adhered with Copper Foil etc. at high temperatures and pressures.No matter be that the thermosetting polyamide acid resin of band crosslinked side base or the polyamide thermoplastic acid resin of band crosslinked side base can be applied in the manufacture of two layers of method single-face flexibility copper-clad board.
Of the present invention should have a definite limitation containing phenylacetylene side base content in the thermoplastic polyimide resin of phenylacetylene side base.Cross-linking reaction can cause polyimides fragility to increase.Crosslink density is crossed senior general and is caused polyimides fragility excessive, is difficult to be applied to the flexible circuit board industry requiring high flexibility and high folding resistance.In the present embodiment, the molecular weight content of described phenylacetylene side base should have 20% of the number-average molecular weight of the polyamic acid resin of phenylacetylene side base lower than described, is preferably 5-15%.
It is worth mentioning that, after the coating completing resin bed in copper-clad plate insulating barrier, what next carry out is the high temperature imidization of polyamic acid resin layer.Temperature-gradient method program is preferably adopted during high temperature imidization, especially should at the high temperature section sufficient dwell time of 350 DEG C-370 DEG C, to ensure the complete imidization when side base is uncrosslinked of this polyamic acid resin layer.If directly enter the high temperature of more than 370 DEG C, then imidization and cross-linking reaction can be carried out simultaneously, and imidization is incomplete because of side base cross-linking reaction may to cause some part in strand, affects final performance.After completing high temperature imidization, also need the high-temperature baking carrying out a period of time more than 370 DEG C, complete crosslinked to make phenylacetylene side base.
Insulating barrier prepared by the present invention is that the single-face flexibility copper-clad board of crosslinked polyimide has more outstanding hot property, dimensional stability and lower water absorption rate relative to the single-face flexibility copper-clad board that non-crosslinked type low thermal expansion coefficient polyimide is made, and can meet procedure for producing and the performance requirement of flexible printed-circuit board better.As everyone knows, Thermocurable polyimide has higher heat endurance, lower water absorption rate and lower thermal coefficient of expansion relative to TPI.Thus, flexibility coat copper plate of the present invention has outstanding properties: the heat decomposition temperature of thermoset polyimide resin is higher, makes single sided board have higher heat endurance and outstanding anti-flammability; The thermal coefficient of expansion of thermoset polyimide resin is lower, and single sided board also can be made in broader temperature range to have less size changing rate, can be applied in the making of meticulousr flexible printed-circuit board; The water absorption rate of thermoset polyimide resin is lower, and the damp and hot processing procedure repeatedly such as etching, baking, development that flexibility coat copper plate can be made to be responsible at flexible electric circuit board has better stability, avoids plate bursting to scrap.
The thickness of above-mentioned insulating barrier used is 10-100 μm, and Copper Foil is electrolytic copper foil, and thickness is 9-70 μm.
Give further to illustrate in detail and describe by following embodiment for the above-mentioned flexibility coat copper plate made, and survey the performances such as its glass transition temperature, thermal coefficient of expansion, anti-flammability, water absorption rate and dimensional stability.
Synthesis containing the polyamic acid resin precursor solution of phenylacetylene side base:
Synthesis example 1
NMP(N-methyl pyrrolidone is added in the there-necked flask of 1L) 500g, weigh the phenylacetylene side base p-phenylenediamine (PPD) of 5.93g, the p-PDA(polyaniline of 18.50g), dissolve in the solution, this solution is cooled in a water bath, adds the BPDA(bibenzene tetracarboxylic dianhydride of 53.66g under nitrogen flowing), then solution is returned to room temperature, Keep agitation 3 hours, carries out polymerisation, prepares thickness polyamic acid solution.With phenylacetylene base on the side chain of this polyamic acid molecule, and phenylacetylene base molecular weight content is 10% of the number-average molecular weight of polymer.
Synthesis example 2
NMP(N-methyl pyrrolidone is added in the there-necked flask of 1L) 500g, weigh the phenylacetylene side base p-phenylenediamine (PPD) of 5.93g, the ODA(4 of 34.24g, 4 '-diaminodiphenyl ether), dissolve in the solution, this solution is cooled in a water bath, add the BPDA(bibenzene tetracarboxylic dianhydride of 53.66g under nitrogen flowing), then solution is returned to room temperature, Keep agitation 3 hours, carry out polymerisation, prepare thickness polyamic acid solution.With phenylacetylene base on this polyamic acid molecular side chain, and phenylacetylene base molecular weight content is 10% of the number-average molecular weight of polymer.
Synthesis example 3
NMP(N-methyl pyrrolidone is added in the there-necked flask of 1L) 500g, weigh the PEMPB(1 of 10.6g, 3-pair-(3-amino-benzene oxygen) benzene-5-(2-phenylacetylene base) benzene), 35.9g APB-N(1,3-pair-(3-amino-benzene oxygen) benzene), dissolve in the solution, this solution is cooled in a water bath, add the BPDA(bibenzene tetracarboxylic dianhydride of 44.6g under nitrogen flowing), then solution is returned to room temperature, Keep agitation 3 hours, carries out polymerisation, prepares thickness polyamic acid solution.With phenylacetylene base on this polyamic acid molecular side chain, and phenylacetylene base molecular weight content is 18% of the number-average molecular weight of polymer.
The synthesis of common polyamide acid resin precursor solution:
Synthesis example 4
NMP(N-methyl pyrrolidone is added in the there-necked flask of 1L) 500g, weigh the p-PDA(polyaniline of 20.55g), dissolve in the solution, this solution is cooled in a water bath, add the BPDA(bibenzene tetracarboxylic dianhydride of 53.66g under nitrogen flowing), then solution is returned to room temperature, Keep agitation 3 hours, carry out polymerisation, prepare thickness polyamic acid solution.This polyamic acid molecular backbone structure is consistent with the polyamic acid backbone structure of gained in synthesis example 1, but not containing phenylacetylene side base.
Synthesis example 5
NMP(N-methyl pyrrolidone is added in the there-necked flask of 1L) 500g, weigh the ODA(4 of 38.05g, 4 '-diaminodiphenyl ether)), dissolve in the solution, this solution is cooled in a water bath, adds the BPDA(bibenzene tetracarboxylic dianhydride of 53.66g under nitrogen flowing), then solution is returned to room temperature, Keep agitation 3 hours, carries out polymerisation, prepares thickness polyamic acid solution.This polyamic acid molecular backbone structure is consistent with the polyamic acid backbone structure of gained in synthesis example 2, but not containing phenylacetylene side base.
Synthesis example 6
NMP(N-methyl pyrrolidone is added in the there-necked flask of 1L) 500g, weigh the APB-N(1 of 43.8g, 3-pair-(3-amino-benzene oxygen) benzene), dissolve in the solution, this solution is cooled in a water bath, adds the BPDA(bibenzene tetracarboxylic dianhydride of 44.6g under nitrogen flowing), then solution is returned to room temperature, Keep agitation 3 hours, carries out polymerisation, prepares thickness polyamic acid solution.This polyamic acid molecular backbone molecular structure is consistent with synthesis example 3 gained polyamic acid backbone structure, but not containing phenylacetylene side base.
Based on above-mentioned synthesis example, to being described below of specific embodiment and comparative example:
Embodiment 1
It is on the electrolytic copper foil of 12 μm that polyamic acid solution obtained for synthesis example 1 is coated on thickness, after coating drying, coating layer thickness is 12 μm, this electrolytic copper foil is placed in high temperature oven 160 DEG C, 200 DEG C, 250 DEG C, 300 DEG C and 350 DEG C and processes 10 minutes respectively, complete imidization, obtained polyimide coating thickness is the single-sided copper foil covered board of 12 μm;
This single-sided copper foil covered board is placed in the high temperature oven being full of nitrogen, oven temperature is 390 DEG C, and toast 30 minutes, discharging, now phenylacetylene base completes crosslinked, thus obtains two layers of method single-face flexibility copper-clad board that insulating barrier is all crosslinked polyimide.
Embodiment 2
It is on the electrolytic copper foil of 12 μm that polyamic acid solution obtained for synthesis example 2 is coated on thickness, after coating drying, coating layer thickness is 12 μm, this electrolytic copper foil is placed in high temperature oven 160 DEG C, 200 DEG C, 250 DEG C, 300 DEG C and 350 DEG C and processes 10 minutes respectively, complete imidization, obtained polyimide coating thickness is the single-sided copper foil covered board of 12 μm;
This single-sided copper foil covered board is placed in the high temperature oven being full of nitrogen, oven temperature is 390 DEG C, and toast 30 minutes, discharging, now phenylacetylene base completes crosslinked, thus obtains two layers of method single-face flexibility copper-clad board that insulating barrier is all crosslinked polyimide.
Embodiment 3
It is on the electrolytic copper foil of 12 μm that polyamic acid solution obtained for synthesis example 3 is coated on thickness, after coating drying, coating layer thickness is 12 μm, this electrolytic copper foil is placed in high temperature oven 160 DEG C, 200 DEG C, 250 DEG C, 300 DEG C and 350 DEG C and processes 10 minutes respectively, complete imidization, obtained polyimide coating thickness is the single-sided copper foil covered board of 12 μm;
This single-sided copper foil covered board is placed in the high temperature oven being full of nitrogen, oven temperature is 390 DEG C, and toast 30 minutes, discharging, now phenylacetylene base completes crosslinked, thus obtains two layers of method single-face flexibility copper-clad board that insulating barrier is all crosslinked polyimide.
Comparative example 1
It is on the electrolytic copper foil of 12 μm that polyamic acid solution obtained for synthesis example 4 is coated on thickness, after coating drying, coating layer thickness is 12 μm, this electrolytic copper foil is placed in high temperature oven 160 DEG C, 200 DEG C, 250 DEG C, 300 DEG C and 350 DEG C and processes 10 minutes respectively, complete imidization, obtained polyimide coating thickness is the single-sided copper foil covered board of 12 μm.
Comparative example 2
It is on the electrolytic copper foil of 12 μm that polyamic acid solution obtained for synthesis example 5 is coated on thickness, after coating drying, coating layer thickness is 12 μm, this electrolytic copper foil is placed in high temperature oven 160 DEG C, 200 DEG C, 250 DEG C, 300 DEG C and 350 DEG C and processes 10 minutes respectively, complete imidization, obtained polyimide coating thickness is the single-sided copper foil covered board of 12 μm.
Comparative example 3
It is on the electrolytic copper foil of 12 μm that polyamic acid solution obtained for synthesis example 6 is coated on thickness, after coating drying, coating layer thickness is 12 μm, this electrolytic copper foil is placed in high temperature oven 160 DEG C, 200 DEG C, 250 DEG C, 300 DEG C and 350 DEG C and processes 10 minutes respectively, complete imidization, obtained polyimide coating thickness is the single-sided copper foil covered board of 12 μm.
The various performance datas of above-described embodiment and comparative example are as shown in table 1 below.
The various performance datas of table 1. single-face flexibility copper-clad board
The method of testing of each characteristic of upper table is as follows:
Tg: glass transition temperature, adopts DMA test, will according to IPC-TM-6502.4.9 method.
CTE: thermal coefficient of expansion, adopts the TMA device of TA company of the U.S., in nitrogen atmosphere, with the heating rate of 10 DEG C/min, and the value between testing 100 DEG C-200 DEG C.
Anti-flammability: detect by UL94 standard.
Dimensional stability: by the test of IPC-TM-6502.2.4 method, wherein "+" represents expansion, and "-" represents contraction, and MD represents the direction that machinery is advanced, and TD represents the direction vertical with MD direction.
In sum, the insulating barrier of two layers of method single-face flexibility copper-clad board of the present invention is crosslinked polyimide resin, while the main chain of this crosslinked polyimide resin bed has certain rigidity, there is certain pliability, and crosslink density can be controlled easily, there is outstanding pliability and resistance to deflection; Low thermal expansion coefficient polyimide with non-crosslinked type is compared, the insulating barrier of two layers of method single-face flexibility copper-clad board of the present invention owing to having the slight degree of cross linking, so have lower water absorption rate, higher dimensional stability and better resistance to dip solderability; The preparation method technique of two layers of method single-face flexibility copper-clad board of the present invention is simple, production efficiency, and cost is low, its two layers of method single-face flexibility copper-clad boards made have good pliability and resistance to deflection, and, there is lower water absorption rate, higher dimensional stability and better resistance to dip solderability.
The above, for the person of ordinary skill of the art, can make other various corresponding change and distortion according to technical scheme of the present invention and technical conceive, and all these change and be out of shape the protection domain that all should belong to the claims in the present invention.
Claims (7)
1. two layers of method single-face flexibility copper-clad board, it is characterized in that, comprise: Copper Foil and the crosslinked polyimide resin bed be located on Copper Foil, described crosslinked polyimide resin bed is by after the polyamic acid resin imidization with phenylacetylene side base, again through Overheating Treatment, make to impel the phenylacetylene side base of polyimide resin to occur crosslinked;
Described in the described molecular weight content with the phenylacetylene side base of the polyamic acid resin of phenylacetylene side base is less than, there is 20% of the number-average molecular weight of the polyamic acid resin of phenylacetylene side base;
The described temperature with the polyamic acid resin imidization of phenylacetylene side base is 330-350 DEG C; Described imidization adopts temperature-gradient method program, at the high temperature section sufficient dwell time of 350 DEG C, to ensure the complete imidization when side base is uncrosslinked of this polyamic acid resin layer.
2. two layers of method single-face flexibility copper-clad board as claimed in claim 1, it is characterized in that, the described synthon with the polyamic acid resin of phenylacetylene side base comprises the aromatic diamine monomers with phenylacetylene side base, described in there is phenylacetylene side base aromatic diamine monomers be the mixture of one or more in following monomer structure:
3. two layers of method single-face flexibility copper-clad board as claimed in claim 1, it is characterized in that, described in there is the phenylacetylene side base of the polyamic acid resin of phenylacetylene side base molecular weight content for described in there is the 5-15% of the number-average molecular weight of the polyamic acid resin of phenylacetylene side base.
4. two layers of method single-face flexibility copper-clad board as claimed in claim 1, is characterized in that, described in there is the polyamic acid resin imidization after-baking of phenylacetylene side base temperature be more than or equal to 370 DEG C.
5. two layers of method single-face flexibility copper-clad board as claimed in claim 1, is characterized in that, described crosslinked polyimide resin layer thickness is 10-100 μm.
6. two layers of method single-face flexibility copper-clad board as claimed in claim 1, is characterized in that, described Copper Foil is electrolytic copper foil, and its thickness is 9-70 μm.
7. a preparation method for two layers of method single-face flexibility copper-clad board as claimed in claim 1, is characterized in that, comprise the steps:
Step 1, synthesis have the polyamic acid resin of phenylacetylene side base;
Step 2, provide Copper Foil, and at one of this Copper Foil, there is described in coating the polyamic acid resin of phenylacetylene side base on the surface;
Step 3, the Copper Foil being coated with the polyamic acid resin with phenylacetylene side base is sent into high temperature oven at the temperature of 330-350 DEG C, carry out imidization obtain single-sided copper foil covered board;
Described imidization adopts temperature-gradient method program, at the high temperature section sufficient dwell time of 350 DEG C, to ensure the complete imidization when side base is uncrosslinked of this polyamic acid resin layer;
Step 4, the single-sided copper foil covered board after this complete imidization to be heat-treated being more than or equal at the temperature of 370 DEG C, obtained two layers of method single-face flexibility copper-clad board.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210335509.2A CN102848643B (en) | 2012-09-11 | 2012-09-11 | Two layers of method single-face flexibility copper-clad board and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210335509.2A CN102848643B (en) | 2012-09-11 | 2012-09-11 | Two layers of method single-face flexibility copper-clad board and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102848643A CN102848643A (en) | 2013-01-02 |
| CN102848643B true CN102848643B (en) | 2016-01-20 |
Family
ID=47395805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210335509.2A Active CN102848643B (en) | 2012-09-11 | 2012-09-11 | Two layers of method single-face flexibility copper-clad board and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102848643B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102417139B1 (en) * | 2016-01-07 | 2022-07-04 | 삼성전자주식회사 | Compensation film and optical film and display device |
| US10988437B1 (en) | 2019-09-30 | 2021-04-27 | United States Of America As Represented By The Secretary Of The Air Force | Bis(aniline) compounds containing multiple substituents with carbon-carbon triple-bonded groups |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5344982A (en) * | 1993-04-02 | 1994-09-06 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Diamines and polyimides containing pendent ethynyl groups |
| US5689004A (en) * | 1995-08-04 | 1997-11-18 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Diamines containing pendent phenylethynyl groups |
| CN101157077A (en) * | 2007-09-18 | 2008-04-09 | 湖北省化学研究院 | A preparation method of gum-free flexible copper-coating plate |
-
2012
- 2012-09-11 CN CN201210335509.2A patent/CN102848643B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5344982A (en) * | 1993-04-02 | 1994-09-06 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Diamines and polyimides containing pendent ethynyl groups |
| US5689004A (en) * | 1995-08-04 | 1997-11-18 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Diamines containing pendent phenylethynyl groups |
| CN101157077A (en) * | 2007-09-18 | 2008-04-09 | 湖北省化学研究院 | A preparation method of gum-free flexible copper-coating plate |
Non-Patent Citations (1)
| Title |
|---|
| 含侧链苯炔基的热固性聚酰亚胺薄膜;高建召等;《应用化学》;20081231;第25卷(第12期);第1413页第1-2段，第1414页第1-2段，第1415页第1-3段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102848643A (en) | 2013-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6129285B2 (en) | Polyimide resin, method for producing the same, and thin film including the same | |
| CN109942815B (en) | Polyimide composite resin with low dielectric constant, preparation method and application | |
| WO2018181436A1 (en) | Polyimide film | |
| CN101754856A (en) | Multilayer polyimide film, laminate and metal-clad laminate | |
| JP7336031B2 (en) | Low dielectric polyimide film and its manufacturing method | |
| JP2017019264A (en) | Metal laminate containing polyimide resin and manufacturing method therefor | |
| KR102346587B1 (en) | Polyimide Film with Improved Dimensional Stability and Method for Preparing the Same | |
| TW202118816A (en) | Polyimide film, method of producing the same, and multilayer film, flexible metal foil laminate and electronic component containing the same | |
| CN104191799A (en) | Method for preparing glue-free double-sided flexible copper-clad plate | |
| JP7509560B2 (en) | Resin films, metal-clad laminates and circuit boards | |
| CN102848643B (en) | Two layers of method single-face flexibility copper-clad board and preparation method thereof | |
| CN105538827A (en) | Two-layer-process double-faced flexible copper-clad plate and production method thereof | |
| CN102848642B (en) | Two layers of method double side flexible copper coated board and preparation method thereof | |
| KR20210084275A (en) | Metal-clad laminate and circuit board | |
| JP4642664B2 (en) | Laminate for wiring board | |
| JP5362752B2 (en) | Polyamic acid composition, polyimide, polyimide film and method for producing them | |
| JP2008303372A (en) | Polyimide precursor having asymmetric structure, polyimide, and their production methods | |
| CN106032406B (en) | polymer, insulating film and flexible copper foil substrate | |
| CN111479395A (en) | Preparation method of glue-free flexible copper-clad plate | |
| JP2019214642A (en) | Polyimide film for coverlay film, and manufacturing method therefor | |
| KR102679927B1 (en) | Polyimide film with high dimensional stability and manufacturing method thereof | |
| JPH0762097A (en) | New copolymer and production thereof | |
| KR100822840B1 (en) | Flexible Copper-Clad Laminate | |
| KR20230068298A (en) | Polyimide film and manufacturing method thereof | |
| CN118317999A (en) | Polyimide film and method for producing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |