CN111533906B - Low-TG high-frequency MPI composition and double-sided high-frequency copper-clad plate thereof - Google Patents
Low-TG high-frequency MPI composition and double-sided high-frequency copper-clad plate thereof Download PDFInfo
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Abstract
The invention relates to the technical field of high polymer materials, in particular to a low-TG high-frequency MPI composition and a double-sided high-frequency copper-clad plate thereof. The low-TG high-frequency MPI composition is prepared from the following components in parts by weight: 22-26 parts of aromatic tetracarboxylic dianhydride, 48-50 parts of long-chain dianhydride, 10-18 parts of aromatic diamine and 190-215 parts of solvent; the low-TG high-frequency MPI composition is coated on a copper foil through a coating process, a high-frequency MPI layer is formed through baking and curing, and then the high-frequency MPI layer is pressed with another copper foil to obtain the double-sided high-frequency copper clad laminate. The invention effectively reduces the glass transition temperature by introducing long-chain dianhydride, improves the processability and the adhesion of the double-sided high-frequency copper-clad plate, reduces the production cost, simultaneously introduces the C = OO structure to effectively reduce the DK and DF values, maintains the electrical property, and ensures that the prepared double-sided high-frequency copper-clad plate has the characteristic of high transmission.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a low-TG high-frequency MPI composition and a double-sided high-frequency copper-clad plate thereof.
Background
With the networking application becoming the mainstream of the market, it is quite common that each terminal electronic product has a network transmission function, and the data transmission speed, whether wired or wireless, is continuously increased, and the transmission frequency of more than 10GHz will become the trend in the future, so the development of high-speed/high-frequency materials becomes the significant research and development of circuit board materials. However, since a generally used Polyimide (PI) material is too soft to be shaped, a Liquid Crystal Polymer (LCP) material is used instead, and a desired 3D flexible board, for example, a curved joint of a robot finger, is manufactured by using plasticity of the LCP material after heating. Therefore, LCP high-frequency flexible boards combining 3D stereo and high-frequency applications are produced. Take LCP material high frequency soft board developed by Mektron of the first major works of Japan as an example: the Dielectric Constant (DK) is 3.0, which is lower than the DK value of the general PI material by about 3.3; the loss Factor (DF) of the material is 0.003, which is lower than the DF value of 0.018 of the common PI material; the water absorption rate of the material is less than 0.04, and is lower than that of a common PI material by 1.5; however, the peel strength of LCP is 0.67kgf/cm, which is inferior to that of PI material of 1.04kgf/cm, and the main application market thereof is focused on the fields of Type C USB connector, 4K high-quality image transmission connector, SATA transmission line, HDMI, antenna, and the like. The most important material property requirements for high speed/high frequency materials are LOW DK/DF and peel strength.
In the prior art, a high-frequency copper-clad plate is prepared by adopting a high-temperature pressing method of a commercially available high-frequency Modified Polyimide (MPI) film or LCP film (as shown in figure 1), but the technology and the cost are mastered on the hands of suppliers, so that the inventor develops a coating pressing method through earlier research, finds a material with LOW DK/DF and high adhesion by utilizing a molecular structure design, and can also be applied to the field of high-speed high-frequency materials. However, although the structure of the invention is not easy to rotate by introducing an ester structure (C = CO) and introducing a large group into the structure, and the structure is compact after stacking to cause a decrease in DK and DF, the processing difficulty and production cost are greatly increased along with an increase in glass transition Temperature (TG) and a decrease in adhesion because the heating temperature required for processing must exceed that of the TG material to start softening, and therefore, the higher the TG, the higher the energy consumption, and the higher the required equipment temperature.
Therefore, it is necessary to find a low-TG high-frequency MPI composition through research so as to solve the problems of TG increase and adhesion decrease while maintaining electrical properties, thereby improving the difficulty in preparing a double-sided high-frequency copper-clad plate and reducing the production cost.
Disclosure of Invention
It is a first object of the present invention to provide a low-TG (glass transition temperature) high-frequency MPI (modified polyimide) composition.
The second purpose of the invention is to provide a double-sided high-frequency copper-clad plate prepared from the low-TG high-frequency MPI composition.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a low-TG high-frequency MPI composition which is prepared from the following components in parts by weight:
the low TG high frequency MPI composition has a solids content of 30wt% and a viscosity of 20000-50000CPS.
Further, the aromatic tetracarboxylic dianhydride is one or two combinations of p-phenylene-ditrimellic dianhydride (TAHQ) and bisphenol A type diether dianhydride (BPADA), and has the following specific structure:
further, the long-chain dianhydride is modified polyimide supplied by Tacostas scientific Co., ltd, model number is AD6, and molecular formula is (C) 60 H 69 O 6 N 2 ) n, molecular weight is 33000-46000.
Further, the aromatic diamine is one or a combination of more than two of 1, 4-phenylene bis (4-Aminobenzoate) (ABHQ), terephthalic acid di-p-aminophenyl ester (BPTP), p-aminobenzoic acid p-aminophenyl ester (APAB) and 4,4' -diaminodiphenyl ether (ODA), and has a specific structure as follows:
further, the solvent is one of N-methyl pyrrolidone (NMP), N-Dimethylacetamide (DMAC), and butyrolactone (GBL).
The invention provides a double-sided high-frequency copper-clad plate prepared from the low-TG high-frequency MPI composition, which comprises copper foils on two sides and a high-frequency MPI layer arranged between the copper foils on the two sides, wherein the high-frequency MPI layer is formed by coating the low-TG high-frequency MPI composition on the surface of the copper foil on one side and heating and cyclizing at high temperature; the thickness of high frequency MPI layer is 12-25um, and the thickness of copper foil is 12-18um.
The third aspect of the invention provides a preparation method of the double-sided high-frequency copper-clad plate, which comprises the following steps:
coating the low-TG high-frequency MPI composition on one side of one copper foil by using two same copper foils through a coating process, and baking and curing to form a high-frequency MPI layer; covering the other part of copper foil on the high-frequency MPI layer, and performing hot-pressing at 200-300 ℃ to obtain the double-sided high-frequency copper-clad plate;
the baking conditions are as follows: keeping the temperature at 140 ℃ for 15min;
the curing conditions are as follows: heating to 150 deg.C for 15min at room temperature, maintaining for 5min, heating to 200 deg.C for 10min, maintaining for 5min, heating to 250 deg.C for 10min, maintaining for 5min, heating to 300 deg.C for 10min, maintaining for 30min, heating to 350 deg.C for 10min, maintaining for 30min, and cooling to room temperature for 60 min.
Further, the copper foil is one of electrolytic copper of TQ-M4-VSP, model CF-T49A-DS-HD2, model JXEFL-BHM, model FL451, model FL-451, model BHFX-92F-HA-V2, model GHY-5-93F-HA-V2, and model GS01, model sexin-gmbh, from mitsui corporation.
The principle of the invention is as follows: by introducing soft chain dianhydride into the structure, TG is reduced, the processability is improved, meanwhile, the adhesion is increased, and by introducing a C = OO structure, DK and DF values are effectively reduced, so that the electric property is maintained.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
according to the preparation method, long-chain dianhydride AD6, aromatic tetracarboxylic dianhydride with a C = OO structure and aromatic diamine are randomly copolymerized to prepare the low-TG high-frequency MPI composition, a coating process is adopted to form a high-frequency MPI layer on the surface of a copper foil, the addition of the long-chain dianhydride AD6 effectively reduces the glass transition temperature, and the processing performance and the adhesion performance of the copper foil are improved, so that the preparation difficulty and the production cost of the double-sided high-frequency copper-clad plate are reduced, the introduction of the C = OO structure effectively reduces DK and DF values, the electrical property is maintained, and the prepared double-sided high-frequency copper-clad plate has the characteristic of high transmission.
Drawings
FIG. 1 is a process flow chart for preparing a double-sided high-frequency copper-clad plate by adopting a commercially available MPI film or LCP film;
FIG. 2 is a process flow diagram of the double-sided high-frequency copper-clad plate of the invention;
FIG. 3 is a process flow chart of the preparation of a double-sided high-frequency copper-clad plate according to embodiments 1 to 8 of the present invention;
FIG. 4 is a process flow chart of the preparation of the double-sided high-frequency copper-clad plate according to the comparative example 1-2.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The aromatic tetracarboxylic dianhydride in the embodiment of the present invention is exemplified by the following, but not limited thereto:
p-phenylene-trimellitate dianhydride, known by the english name p-phenylenebis (trimetallite anhydride), abbreviated as TAHQ, CAS number 2770-49-2;
bisphenol A type diether dianhydride, known by the English name 4,4'- (4, 4' -Isopropylidenediphyxy) bis (phthalic anhydride), abbreviated BPADA and having CAS number 38103-06-9.
The following long-chain dianhydrides are exemplified in the examples of the invention, but not limited thereto:
modified polyimide, the English name of which is Solvent soluble thermoplastic polyimide resin and organic derivatives from raw materials, model number of AD6, and molecular formula (C) 60 H 69 O 6 N 2 ) n, a molecular weight of 33000-46000, from Tacostas scientific, having the physical properties shown in Table 1 below:
TABLE 1
The following aromatic diamines are exemplified in the examples of the present invention, but not limited thereto:
1, 4-phenylenebis (4-aminobenzoate), english name [4- (4-aminobenzoyl) oxyphenyl ]4-aminobenzoate, abbreviation ABHQ, CAS number 22095-98-3;
di-p-aminophenyl terephthalate, known by the English name Bis (4-aminophenyl) tert-plate, abbreviated BPTP, having CAS number 169926-73-1;
p-aminobenzoate, english name 4-Aminophenyl-4-aminobenzoate, abbreviation APAB, CAS number 20610-77-9;
4,4 '-diaminodiphenyl ether, english name 4,4' -Oxydianiline, abbreviation ODA, CAS number 101-80-4.
The solvent in the embodiment of the invention is preferably N-methylpyrrolidone, the name of England is N-methyl-2-pyrollidone, the abbreviation is NMP, and the CAS number is 872-50-4, but not limited to the above;
the low-TG, high-frequency MPI compositions prepared in the examples according to the invention have a solids content of 30 wt.% and a viscosity of 20000 to 50000CPS, where the starting materials and amounts used in examples 1 to 4 and comparative example 1 are indicated in Table 2 below:
TABLE 2
Example 1
Adding NMP and ABHQ into a 500mL reaction bottle according to the proportion shown in Table 2, stirring until the NMP and the ABHQ are dissolved, adding BPADA and AD6, stirring and reacting for 6 hours, and stirring and dissolving to prepare the low-TG high-frequency MPI composition.
Example 2
Adding NMP and BPBT into a 500mL reaction bottle according to the mixture ratio shown in Table 2, stirring until the NMP and the BPBT are dissolved, adding BPADA and AD6, stirring for reacting for 6 hours, and stirring for dissolving to prepare the low-TG high-frequency MPI composition.
Example 3
Adding NMP and APAB into a 500mL reaction bottle according to the proportion shown in Table 2, stirring until the NMP and the APAB are dissolved, adding BPADA and AD6, stirring, reacting for 12 hours, and stirring to dissolve to obtain the low-TG high-frequency MPI composition.
Example 4
Adding NMP and ODA into a 500mL reaction bottle according to the proportion shown in Table 2, respectively, stirring until the NMP and the ODA are dissolved, then adding BPADA and AD6, stirring for reacting for 12 hours, and stirring for dissolving to obtain the low-TG high-frequency MPI composition.
Comparative example 1
Adding NMP and ABHQ into a 500mL reaction bottle according to the mixture ratio shown in Table 2, stirring until the NMP and the ABHQ are dissolved, adding BPADA, stirring for reaction for 6 hours, and stirring for dissolution to obtain the high-frequency MPI composition of the comparative example 1.
The following table 3 shows the raw materials and the amounts used in examples 5 to 8 according to the invention and comparative example 2:
TABLE 3
Example 5
Adding NMP and ABHQ into a 500mL reaction bottle according to the proportion shown in Table 3, stirring until the NMP and the ABHQ are dissolved, adding TAHQ and AD6, stirring for reacting for 12 hours, and stirring for dissolving to obtain the low-TG high-frequency MPI composition.
Example 6
Adding NMP and BPBT into a 500mL reaction bottle according to the proportion shown in the table 3 respectively, stirring until the NMP and the BPBT are dissolved, adding TAHQ and AD6, stirring for reacting for 12 hours, and stirring for dissolving to obtain the low-TG high-frequency MPI composition.
Example 7
Adding NMP and APAB into a 500mL reaction bottle according to the proportion shown in Table 3, stirring until the NMP and the APAB are dissolved, adding TAHQ and AD6, stirring for reaction for 12 hours, and stirring for dissolution to obtain the low-TG high-frequency MPI composition.
Example 8
Adding NMP and ODA into a 500mL reaction bottle according to the proportion shown in Table 3, stirring until the NMP and the ODA are dissolved, adding TAHQ and AD6, stirring for reacting for 12 hours, and stirring for dissolving to obtain the low-TG high-frequency MPI composition.
Comparative example 2
Adding NMP and ABHQ into a 500mL reaction bottle according to the mixture ratio shown in Table 3, respectively, stirring until the NMP and the ABHQ are dissolved, adding TAHQ, stirring for reaction for 12 hours, and stirring for dissolution to obtain the high-frequency MPI composition of the comparative example 2.
Preparation of double-sided high-frequency copper-clad plate of examples 1 to 8
As shown in fig. 2-3, the preparation method of the double-sided high-frequency copper-clad plate prepared from the low-TG high-frequency MPI composition disclosed by the invention comprises the following steps:
two parts of the same copper foil are taken, the copper foil is of the type BHM-102F-HA-V2, and the thickness is 12um (Nippon Nissan metals Co., ltd.); coating the low-TG high-frequency MPI composition prepared in examples 1 to 8 on one side of a copper foil by a coating process, and baking and curing to form a high-frequency MPI layer; covering the other part of copper foil on the high-frequency MPI layer, and performing hot-pressing (at the temperature of 200-300 ℃) to obtain the double-sided high-frequency copper-clad plate; wherein the baking conditions are as follows: preserving the heat for 15min at 140 ℃; the curing conditions are as follows: heating to 150 deg.C for 15min at room temperature, maintaining for 5min, heating to 200 deg.C for 10min, maintaining for 5min, heating to 250 deg.C for 10min, maintaining for 5min, heating to 300 deg.C for 10min, maintaining for 30min, heating to 350 deg.C for 10min, maintaining for 30min, and cooling to room temperature for 60 min.
The double-sided high-frequency copper-clad plate comprises copper foils on two sides and a high-frequency MPI layer arranged between the copper foils on the two sides, wherein the high-frequency MPI layer is formed by coating the low-TG high-frequency MPI composition on the surface of the copper foil on one side and heating and cyclizing at high temperature; the thickness of high frequency MPI layer is 12-25um, and the thickness of copper foil is 12-18um.
Preparation of double-sided high-frequency copper-clad plate according to comparative examples 1-2
As shown in FIG. 4, two identical copper foils, each having a copper foil type of BHM-102F-HA-V2 and a thickness of 12um (Nippon Nissan Metal Co., ltd.), were used; coating the high-frequency MPI composition of the comparative example 1 or 2 on one side of a part of copper foil through a coating process, and baking and curing to form a high-frequency MPI layer; covering the other part of copper foil on the high-frequency MPI layer, and performing hot-pressing (at the temperature of 400-500 ℃) to obtain the double-sided high-frequency copper-clad plate; wherein the baking conditions are as follows: keeping the temperature at 140 ℃ for 15min; the curing conditions are as follows: heating to 150 deg.C for 15min at room temperature, maintaining for 5min, heating to 200 deg.C for 10min, maintaining for 5min, heating to 250 deg.C for 10min, maintaining for 5min, heating to 300 deg.C for 10min, maintaining for 30min, heating to 350 deg.C for 10min, maintaining for 30min, and cooling to room temperature for 60 min.
The double-sided high-frequency copper-clad plate comprises copper foils on two sides and a high-frequency MPI layer arranged between the copper foils on the two sides, wherein the high-frequency MPI layer is formed by coating the high-frequency MPI composition of the comparative example 1 or the comparative example 2 on the surface of the copper foil and heating and cyclizing at high temperature; the thickness of high frequency MPI layer is 12-25um, and the thickness of copper foil is 12-18um.
Preparation of double-sided high-frequency copper-clad plate of comparative example 3
Two identical copper foils with the type of BHM-102F-HA-V2 and the thickness of 12um (purchased from Nippon Nissan metals Co., ltd.) were taken; a commercial high-frequency MPI film (purchased from Kaneka company, model number SR # SW, thickness 25 um) is stacked between two copper foils, and the double-sided high-frequency copper-clad plate is obtained through hot-pressing (temperature is 300-380 ℃).
Preparation of double-sided high-frequency copper-clad plate of comparative example 4
Two identical copper foils were taken, the copper foils being of the type BHM-102F-HA-V2 and having a thickness of 12um (available from Nippon Nissan metals Co., ltd.); a commercially available LCP film (purchased from Kuraray company, the model is CT-Q, the thickness is 25 um) is stacked between two copper foils, and the double-sided high-frequency copper-clad plate is obtained through hot pressing (the temperature is 300-380 ℃).
Performance testing
The double-sided high-frequency copper-clad plates prepared in examples 1 to 8 and comparative examples 1 to 4 were subjected to DK and DF tests, glass transition Temperature (TG) tests, peel strength tests and floating tin tests, respectively, and the test standards and test conditions were as follows:
1. DK and DF test
(1) And (4) testing standard: IPC-TM 650.5.5.13;
(2) And (3) testing conditions are as follows: sample size: 7cm (width) × 12cm (length); 10GHz;
2. glass transition Temperature (TG) test
(1) And (4) testing standard: IPC-TM 650.4.24.5 method B;
(2) And (3) testing conditions are as follows: sample size: 2mm (wide) × (15-20) mm (long); stretching tension: 2g (20 mN); temperature rise rate: 10 ℃/min;
3. test of Peel Strength
(1) And (4) testing standard: IPC-TM 650.4.9 method A;
(2) And (3) testing conditions are as follows: sample size: type A-Ethed Specifen (3.2 mm wide); stretching speed: 50.8mm/min
4. Tin bleaching test
(1) And (4) testing standard: IPC-TM 650.4.13;
(2) The judgment basis is as follows: a PASS (PASS) was maintained at 320 ℃ for 10 sec.
Data of the performance tests of examples 1 to 4 and comparative examples 1 and 3 are described in the above table 2, and data of the performance tests of examples 5 to 8 and comparative examples 2 and comparative example 4 are described in the above table 3.
As can be seen from the data in tables 2 and 3, examples 1-8 and comparative examples 1-4 both passed the tin-bleaching test; the electrical properties of examples 1 to 8 were good, and all of them had TG <300 ℃ (the ordinary PI had TG ≧ 300 ℃ and poor processability), and all of them had peel strength >0.5Kgf/cm (the ordinary peel strength was not more than 0.5 Kgf/cm).
In table 2, the reason why the DK and DF of comparative example 1 are higher than those of example 1 indicates that the electrical property of comparative example 1 is inferior to that of example 1, and the TG of comparative example 1 is 336 ℃ much higher than that of example 1, so that the processability of comparative example 1 is poor, and the peel strength is also poor to 0.42Kgf/cm as the TG of comparative example 1 becomes higher, is that it cannot meet the application requirements, is that long-chain dianhydride AD6 is added to example 1, increasing the flexibility of the molecular chain, thereby effectively reducing TG, and the excellent adhesion and electrical property of AD6 makes it possible to prepare a high-frequency MPI composition capable of improving the peel strength and maintaining the electrical property when preparing a copper-clad plate, as also confirmed by the test results of example 5 and comparative example 2 in table 3.
In addition, it can be seen from the test results of examples 1 to 4 and examples 5 to 8 that example 5 is the best example, and the aromatic tetracarboxylic dianhydride selected in example 5 introduces C = OO structure for TAHQ and aromatic diamine ABHQ, so that the structure can be stacked tightly, the values of DK and DF can be effectively reduced, and the peel strength can be greatly improved and the electrical property can be maintained when TG is reduced after the aromatic tetracarboxylic dianhydride is matched with long-chain dianhydride AD 6.
The foregoing shows and describes the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A low-TG high-frequency MPI composition is characterized by being prepared from the following components in parts by weight:
the long-chain dianhydride is modified polyimide with the model of AD6 and the molecular formula of (C) 60 H 69 O 6 N 2 ) n, molecular weight 33000-46000，
The low-TG high-frequency MPI composition has a solids content of 30 wt.% and a viscosity of 20000 to 50000CPS.
2. The low-TG high-frequency MPI composition according to claim 1, wherein the aromatic tetracarboxylic dianhydride is one or a combination of two of p-phenylene-bistrimelliate dianhydride and bisphenol-A diether dianhydride.
3. The low-TG, high-frequency MPI composition according to claim 1, wherein said aromatic diamine is one or a combination of two or more of 1, 4-phenylene bis (4-aminobenzoate), di-p-aminophenyl terephthalate, p-aminobenzoate, 4' -diaminodiphenyl ether.
4. The low-TG, high-frequency MPI composition according to claim 1, wherein the solvent is one of N-methylpyrrolidone, N-dimethylacetamide and butyrolactone.
5. A double-sided high-frequency copper-clad plate prepared from the low-TG high-frequency MPI composition according to any one of claims 1 to 4, which is characterized by comprising copper foils at two sides and a high-frequency MPI layer arranged between the copper foils at two sides, wherein the high-frequency MPI layer is formed by coating the low-TG high-frequency MPI composition on the surface of one copper foil and heating and cyclizing at high temperature; the thickness of the high-frequency MPI layer is 12-25 mu m, and the thickness of the copper foil is 12-18 mu m.
6. The method for preparing a double-sided high-frequency copper-clad plate prepared from the low-TG high-frequency MPI composition according to claim 5, comprises the following steps:
coating the low-TG high-frequency MPI composition on one side of one copper foil by using two parts of the same copper foil through a coating process, and baking and curing to form a high-frequency MPI layer; covering the other part of copper foil on the high-frequency MPI layer, and performing hot-pressing at 200-300 ℃ to obtain the double-sided high-frequency copper-clad plate;
the baking conditions are as follows: preserving the heat for 15min at 140 ℃;
the curing conditions are as follows: heating to 150 deg.C for 15min at room temperature, maintaining for 5min, heating to 200 deg.C for 10min, maintaining for 5min, heating to 250 deg.C for 10min, maintaining for 5min, heating to 300 deg.C for 10min, maintaining for 30min, heating to 350 deg.C for 10min, maintaining for 30min, and cooling to room temperature for 60 min.
7. The method for preparing a double-sided high-frequency copper-clad plate prepared from the low-TG high-frequency MPI composition according to claim 6, wherein the copper foil is one of electrolytic copper of TQ-M4-VSP of Japan Trigonopsis metal mining corporation, electrolytic copper of CF-T49A-DS-HD2 of Japan Futian Metal foil powder Industrial corporation, electrolytic copper of JXEFL-BHM of Japan Nikkaido metal corporation, electrolytic copper of FL451 of gold development copper foil Co., ltd, calendered copper of BHFX-92F-HA-V2 of Japan Nikkaido metal corporation, calendered copper of GHY5-93F-HA-V2 of Japan Nikkaido metal corporation, calendered copper of GS01 of Taikkaido science Co.
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| US7842124B2 (en) * | 2006-08-08 | 2010-11-30 | Exxonmobil Research And Engineering Company | Polymer membrane for separating aromatic and aliphatic compounds |
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| JPH08294993A (en) * | 1995-04-27 | 1996-11-12 | Kanegafuchi Chem Ind Co Ltd | Flexible copper plated laminate board |
| CN109337072A (en) * | 2018-09-26 | 2019-02-15 | 江阴骏驰复合材料有限公司 | A kind of polymeric composition, copper-clad plate and the circuit board of low DK and DF |
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