CN1924088A - Polyimide polymer for preparing copper-cover laminated plate and preparation method thereof - Google Patents
Polyimide polymer for preparing copper-cover laminated plate and preparation method thereof Download PDFInfo
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- CN1924088A CN1924088A CN 200510098509 CN200510098509A CN1924088A CN 1924088 A CN1924088 A CN 1924088A CN 200510098509 CN200510098509 CN 200510098509 CN 200510098509 A CN200510098509 A CN 200510098509A CN 1924088 A CN1924088 A CN 1924088A
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- copper
- laminated plate
- dianhydride
- polyimide polymer
- cover laminated
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Abstract
The invention discloses a polyimide polymer and preparing method of clad copper layer board, which comprises the following steps: dissolving aromatic tetracarboxylic dianhydride and aromatic diamine in the polar aprotic solvent without adding inorganic filler; producing polyamide acid solution; proceeding amination reaction for polyamide acid solution to obtain the product with heat bulking coefficient between 10 and 30pm/deg.c.
Description
Technical field
The invention relates to a kind of polyimide polymer and preparation method thereof, and particularly relevant for a kind of polyimide polymer of preparing copper-cover laminated plate and preparation method thereof that is used to.
Background technology
Flexible printed wiring board has been widely used in as consumption electronic products such as notebook computer, mobil phone, personal digital assistant and digital still cameras, along with consumption electronic products move towards compact trend gradually, flexible printed wiring board is also towards using more frivolous no glue formula polyimide copper-clad laminated board development.
Whether there to be one deck adhesion agent layer between polyimide layer and the Copper Foil is classification, and the polyimides flexible printed circuit board (PCB) can be divided into glue and no glue formula.Generally speaking, polyimide polymer is not good to the then property of Copper Foil, so have the polyimides flexible printed circuit board (PCB) of glue formula can be between polyimide mould layer and Copper Foil be that resin is then fixing with it as adhesion agent layer with Resins, epoxy or acryl, the polyimides flexible printed circuit board (PCB) that does not have the glue formula then is directly then in copper foil surface with polyimide, this polyimide polymer must be selected the incompatible synthetic polymer of suitable set of monomers for use, or just can be used as the polyimide polymer material of the copper-cover laminated plate of no glue formula through suitable upgrading.
The copper-cover laminated plate of no glue formula mainly is the polyamic acid precursor that utilizes with polyimide, usually prepare by the monomer chemical reaction of aromatic tetracarboxylic acid's dianhydride and aromatic diamine, the polyamic acid precursor is coated the surface of Copper Foil, heat the solvent that removes polyamic acid again, continue heating and makes the inferior amidation of polyamic acid generate polyimide layer, it is characterized in that to combine with adhesion agent layer between polyimide layer and the Copper Foil at copper foil surface with high temperature.
In the production process of flexible printed wiring board, copper-cover laminated plate or the flexible printed wiring board that carried out etching program all must be smooth, because in making processes, flexible printed wiring board can be through the slit of many equipment, if flexible printed wiring board has curled, will cause flexible printed wiring board can't pass through the equipment slit smoothly, and make whole processing procedure interrupt.
Therefore, the polyimides flexible printed circuit board (PCB) regular meeting of commonly using adds inorganic filler in prescription, with the thermal expansion coefficient difference that furthers between polyimide layer and the Copper Foil, avoids the generation of curling phenomenon.Yet, though add the flatness that inorganic filler has improved base material, be convenient to manufacturing of flexible printed wiring board, but cause flexible printed wiring board on the contrary when bending repeatedly, the polyimide layer problems such as transparency variation of (that is the anti tear degree is relatively poor), anti-bending reduction and flexible printed wiring board of more easily breaking, thereby be unfavorable for the use of opto-electronics user optical registration processing procedure.
So how improving the tear strength of polyimides flexible printed circuit board (PCB), anti-bending and the transparency is to have the knack of the problem that this skill person institute desire solves.
This shows that above-mentioned existing polyimide polymkeric substance and preparation method thereof obviously still has inconvenience and defective, and demands urgently further being improved in product, manufacture method and use.In order to solve the problem that polyimide polymer and preparation method thereof exists, relevant manufacturer there's no one who doesn't or isn't seeks solution painstakingly, but do not see always that for a long time suitable design finished by development, and common product and manufacture method do not have appropriate method to address the above problem, and this obviously is the problem that the anxious desire of relevant dealer solves.Therefore how to found a kind of new polyimide polymer for preparing copper-cover laminated plate and preparation method thereof that is used to, just become the current industry utmost point to need improved target.
Because the defective that above-mentioned existing polyimide polymkeric substance and preparation method thereof exists, the inventor is based on being engaged in this type of product design manufacturing abundant for many years practical experience and expertise, and the utilization of cooperation scientific principle, actively studied innovation, in the hope of founding a kind of new polyimide polymer for preparing copper-cover laminated plate and preparation method thereof that is used to, can improve general existing polyimide polymkeric substance and preparation method thereof, make it have more practicality.Through constantly research, design, and after studying repeatedly and improving, create the present invention who has practical value finally.
Summary of the invention
The objective of the invention is to, overcome the defective that the existing polyimide polymkeric substance exists, and a kind of new polyimide polymer that is used to prepare copper-cover laminated plate is provided, technical problem to be solved is it to be applicable to make the polyimide copper-clad laminated plates, is particularly useful for making the copper-cover laminated plate of no glue formula.It is that the polyimide polymer that will not contain inorganic filler directly is coated on copper foil surface, forms the good copper-cover laminated plate of tear strength, thereby is suitable for practicality more.
Another object of the present invention is to, a kind of polyimide polymer that is used to prepare copper-cover laminated plate is provided, technical problem to be solved is to make it provide a kind of anti-bending good polyimide polymer, is applicable to the copper-cover laminated plate of making no glue formula.The polyimide polymer that does not contain inorganic filler directly is coated on copper foil surface, forms the good copper-cover laminated plate of anti-bending, thereby be suitable for practicality more.
A further object of the present invention is, a kind of polyimide polymer that is used to prepare copper-cover laminated plate is provided, and technical problem to be solved is to make its transparency good, is applicable to the copper-cover laminated plate of making no glue formula.The polyimide polymer that does not contain inorganic filler directly is coated on copper foil surface, forms the dielectric layer of the good copper-cover laminated plate of the transparency, thereby be suitable for practicality more.
An also purpose of the present invention is, a kind of polyimide polymer that is used to prepare copper-cover laminated plate is provided, technical problem to be solved is to make it have dimensional stability, is applicable to make the polyimide copper-clad laminated plates, does not especially have the polyimide copper-clad laminated plates of glue formula.It is to prepare polyamic acid solution by the ratio that changes aromatic tetracarboxylic acid's dianhydride or aromatic diamine, polyamic acid solution is produced polyimide polymer thus again, the polyimide polymer that is produced has the thermal expansivity close with Copper Foil, make the polyimide copper-clad laminated plates that preferable stability be arranged, meet the dimensional stability of institute's standard among the IPC-4204.In addition, not needing to use Resins, epoxy or acryl between polyimide layer and the Copper Foil is that resin is as solid, so do not have the problem of flexible printed wiring board non-refractory in high temperature process of commonly using, thereby be suitable for practicality more, and have the utility value on the industry.
Another purpose of the present invention is that a kind of method for preparing polyimide polymer is being provided, especially can be used for preparing the method for the polyimide polymer of copper-cover laminated plate about a kind of preparation, technical problem to be solved is to make it by the ratio that changes aromatic tetracarboxylic acid's dianhydride and aromatic diamine, obtains the polyimide polymer close with the thermal expansivity of Copper Foil.Under comparing with the polyimide polymer with inorganic filler, its stripping strength (Peel Strength) is suitable, thereby is suitable for practicality more.
Another object of the present invention is to, a kind of method for preparing copper-cover laminated plate is provided, technical problem to be solved is to make it prepare polyamic acid solution by the monomer chemical reaction of aromatic tetracarboxylic acid's dianhydride and aromatic diamine, again polyamic acid solution is coated copper foil surface, heat and make the inferior amidation of polyamic acid generate polyimide layer at copper foil surface, make copper-cover laminated plate, thereby be suitable for practicality more.
The present invention compared with prior art has tangible advantage and beneficial effect.By above technical scheme as can be known, the present invention's polyimide polymer of being used to prepare copper-cover laminated plate and preparation method thereof has following advantage at least:
By method of the present invention, can obtain having the polyimide copper-clad laminated plates of good dimensional stability and preferable tear strength, anti-bending and the transparency.
In sum, the present invention is special is used to polyimide polymer for preparing copper-cover laminated plate and preparation method thereof, it has above-mentioned many advantages and practical value, and in like product and manufacture method, do not see have similar design to publish or use and really genus innovation, no matter it is at product, bigger improvement is all arranged on the manufacture method or on the function, have large improvement technically, and produced handy and practical effect, and the multinomial effect that has enhancement than existing polyimide polymkeric substance and preparation method thereof, thereby being suitable for practicality more, really is a novelty, progressive, practical new design.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technique means of the present invention, and can be implemented according to the content of specification sheets, and for above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, below especially exemplified by preferred embodiment, and conjunction with figs., be described in detail as follows.
Description of drawings
Fig. 1 a shows specimen coding 8, is to be the test result of known polyimide polymer transparency, and it adds inorganic filler in the preparation process of polyimide polymer.
Fig. 1 b shows specimen coding 7, is the test result for polyimide polymer transparency of the present invention, and it does not add inorganic filler in the preparation process of polyimide polymer.
Embodiment
Reach technique means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with accompanying drawing and preferred embodiment, the polyimide polymer and preparation method thereof its embodiment, manufacture method, step, feature and the effect thereof that foundation the present invention are prepared being used to of proposing copper-cover laminated plate, describe in detail as after.
The preparation of polyimide polymer of the present invention is that aromatic tetracarboxylic acid's dianhydride and aromatic diamine are dissolved in reaction generation polyamic acid solution in the polar aprotic solvent, inferior amidation forms the heat resistant poly imide polymer to polyamic acid solution via heat treated, under the condition of not adding any inorganic filler, the not ear ratio of various aromatic tetracarboxylic acid's dianhydrides or various aromatic diamines in the adjustment polyamic acid solution, the thermal expansivity that makes polyimide polymer is between about 10 to about 30ppm/ ℃.
In one embodiment of this invention, aromatic diamine is to select the different not Ursol D and the diamines yl diphenyl ethers of ear mixed for use, and aromatic tetracarboxylic acid's dianhydride is to select the diphenyl tetracarboxylic dianhydride for use.The solvent N-Methyl pyrrolidone is poured in 35 ℃ of reactive tanks, while stirring Ursol D and diamines yl diphenyl ether are added in the reactive tank, wherein the not ear ratio of Ursol D and diamines yl diphenyl ether is about 0.1 to about 10.0, is preferably about 1.0 to about 5.0.Stir after 12 hours, while stirring the diphenyl tetracarboxylic dianhydride is slowly added in the reactive tank, stirred overnight obtains polyamic acid solution.This polyamic acid solution is coated copper foil surface, carry out inferior amidation to form polyimide polymer via heat treated, described polyimide polymer can generate stable on heating polyimide layer at copper foil surface, promptly obtains the copper-cover laminated plate that can be used for flexible printed wiring board of the present invention.
According to other embodiments of the invention, aromatic diamine preferably is selected from Ursol D, diamines yl diphenyl ether, pentanoic methane and two amido benzophenone, and aromatic tetracarboxylic acid's dianhydride preferably is selected from diphenyl tetracarboxylic dianhydride, pyromellitic acid dianhydride and benzophenone tetracarboxylic dianhydride.
Polyimide polymer of the present invention has good thermotolerance, its thermal expansivity is about 15 to about 27ppm/ ℃, owing near thermal expansivity 18ppm/ ℃ of Copper Foil, therefore have good then effect, be suitable for producing no glue formula copper-cover laminated plate for copper foil surface.
Above-claimed cpd is as illustration, be not in order to limit the present invention, have the knack of this skill person and can need select suitable aromatic tetracarboxylic acid's dianhydride and aromatic diamine kind for use according to it, and select suitable not ear ratio for use, as long as the thermal expansivity that can make resulting polyimide polymer is between about 10 to about 30ppm/ ℃, preferably between about 15 to about 27ppm/ ℃.
In sum, the present invention only uses single two anhydride components, and does not need to add inorganic filler, has not only simplified the reaction process that forms polyimide polymer, also still can reach among the IPC-4204 for dimensional stability and for the requirement of stripping strength.
In addition, polyimide polymer of the present invention and copper-cover laminated plate also have preferable anti-bending, see table 1:
Table 1: the test result of anti-bending
| Specimen coding | Total thickness (micron) | Bending number of times (ten thousand times) | |
| Back-adhesive film is in inside | Back-adhesive film externally | ||
| 1 | 31 | 5,000 | 5,000 |
| 2 | 31 | 3,610 | 3,240 |
| 3 | 43 | 2,530 | 2,050 |
| 4 | 43 | 1,500 | 1,050 |
The above-mentioned property testing of anti-the bending is to adopt the sample of two groups of different thickness to detect, and wherein, 1 and 3 for not adding the copper-cover laminated plate of inorganic filler, and 2 and 4 for adding the copper-cover laminated plate of inorganic filler.No matter back-adhesive film is positioned at inside or outside, and in the sample of same thickness, what do not add bending number of times all more known (the interpolation inorganic filler is promptly arranged) that the copper-cover laminated plate of inorganic filler can bear is many.
Polyimide polymer of the present invention and copper-cover laminated plate also have preferable tear strength, see table 2:
Table 2: the test result of tear strength
| Specimen coding | The thickness of polyimide layer (micron) | Initial tear resistance (gram) |
| 5 | 12.5 | 1100 |
| 6 | 12.5 | 720 |
| 7 | 25 | 2200 |
| 8 | 25 | 1500 |
Above-mentioned tear strength test is to adopt the sample of two groups of different thickness to detect according to the 2.4.16 method of IPC-TM-650, and wherein, 5 and 7 for not adding the copper-cover laminated plate of inorganic filler, and 6 and 8 for adding the copper-cover laminated plate of inorganic filler.In the sample of same thickness, do not add initial tear resistance all more known (the interpolation inorganic filler is promptly arranged) that the copper-cover laminated plate of inorganic filler can bear for big.
Polyimide polymer of the present invention also has the preferable transparency, sees also shown in Fig. 1 a and Fig. 1 b.Fig. 1 a shows specimen coding 8, is to be the test result of known polyimide polymer transparency, and it adds inorganic filler in the preparation process of polyimide polymer.Fig. 1 b shows specimen coding 7, is the test result for polyimide polymer transparency of the present invention, and it does not add inorganic filler in the preparation process of polyimide polymer.In comparison, the transparency of not adding the resulting polyimide polymer of inorganic filler of the present invention obviously is known as good.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the method that can utilize above-mentioned announcement and technology contents are made a little change or be modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (8)
1, a kind of method for preparing copper-cover laminated plate, this copper-cover laminated plate is to be used to prepare flexible printed wiring board, it is characterized in that this method may further comprise the steps:
Aromatic tetracarboxylic acid's dianhydride and aromatic diamine are dissolved in the polar aprotic solvent, need not add inorganic filler, generate polyamic acid solution with reaction;
This polyamic acid solution is coated on the Copper Foil; And
Heat this polyamic acid solution and form polyimide layer to carry out inferior amidate action on this Copper Foil, wherein the thermal expansivity of this polyimide layer is between about 10 to about 30ppm/ ℃.
2, method according to claim 1 is characterized in that wherein said aromatic tetracarboxylic acid's dianhydride is to be selected from the group that diphenyl tetracarboxylic dianhydride, pyromellitic acid dianhydride and benzophenone tetracarboxylic dianhydride are formed.
3, method according to claim 1 is characterized in that wherein said aromatic diamine is selected from the group that Ursol D, diamines yl diphenyl ether, pentanoic methane and two amido benzophenone are formed.
4, method according to claim 2 is characterized in that wherein said aromatic tetracarboxylic acid's dianhydride is the diphenyl tetracarboxylic dianhydride.
5, method according to claim 3 is characterized in that wherein said aromatic diamine is prepared by mixing Ursol D and diamines yl diphenyl ether.
6, method according to claim 5, the not ear ratio that it is characterized in that wherein said Ursol D and this diamines yl diphenyl ether is about 0.1 to about 10.0.
7, method according to claim 6, the not ear ratio that it is characterized in that wherein said Ursol D and this diamines yl diphenyl ether is about 1.0 to about 5.0.
8, a kind of according to the prepared copper-cover laminated plate of the described method of each claim in the claim 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200510098509 CN1924088A (en) | 2005-08-31 | 2005-08-31 | Polyimide polymer for preparing copper-cover laminated plate and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510098509 CN1924088A (en) | 2005-08-31 | 2005-08-31 | Polyimide polymer for preparing copper-cover laminated plate and preparation method thereof |
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| CN1924088A true CN1924088A (en) | 2007-03-07 |
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| CN 200510098509 Pending CN1924088A (en) | 2005-08-31 | 2005-08-31 | Polyimide polymer for preparing copper-cover laminated plate and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100129552A1 (en) * | 2008-11-21 | 2010-05-27 | Infineon Technologies Ag | Low viscosity polymeric printing solutions and electronic components bearing polyimide based upon the low viscosity polymeric printing solutions |
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2005
- 2005-08-31 CN CN 200510098509 patent/CN1924088A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100129552A1 (en) * | 2008-11-21 | 2010-05-27 | Infineon Technologies Ag | Low viscosity polymeric printing solutions and electronic components bearing polyimide based upon the low viscosity polymeric printing solutions |
| CN101752325A (en) * | 2008-11-21 | 2010-06-23 | 英飞凌科技股份有限公司 | Low viscosity polymeric printing solutions and electronic components bearing polyimide based upon the low viscosity polymeric printing solutions |
| CN101752325B (en) * | 2008-11-21 | 2013-06-26 | 英飞凌科技股份有限公司 | Low viscosity polymeric printing solutions and electronic components bearing polyimide based upon the low viscosity polymeric printing solutions |
| US9313898B2 (en) * | 2008-11-21 | 2016-04-12 | Infineon Technologies Ag | Low viscosity polymeric printing solutions and electronic components bearing polyimide based upon the low viscosity polymeric printing solutions |
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