CN111533906A - 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
- Publication number
- CN111533906A CN111533906A CN202010468663.1A CN202010468663A CN111533906A CN 111533906 A CN111533906 A CN 111533906A CN 202010468663 A CN202010468663 A CN 202010468663A CN 111533906 A CN111533906 A CN 111533906A
- Authority
- CN
- China
- Prior art keywords
- frequency
- copper
- mpi
- low
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/08—Interconnection of layers by mechanical means
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/24—Organic non-macromolecular coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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 215 parts of solvent 190-; 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 adhesiveness of the double-sided high-frequency copper-clad plate, reduces the production cost, simultaneously reduces the DK and the DF value by introducing C-OO structural effect, 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 is less than 0.04 and is lower than the water absorption rate of 1.5 of the common PI material; however, the peel strength LCP is 0.67kgf/cm, which is inferior to the peel strength 1.04kgf/cm of the general PI material, and the main application market thereof is focused on the fields of Type CUSB 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 made of a commercially available high-frequency Modified Polyimide (MPI) film or LCP film by a high-temperature pressing method (as shown in fig. 1), but the technology and the cost are mastered by suppliers, so that the inventor develops a coating pressing method through earlier research, finds a LOW DK/DF and a material with high adhesion by utilizing a molecular structure design, and can also be applied to the field of high-speed high-frequency materials, and the achievement is disclosed in a patent of a LOW DK and DF polymer composition, a copper-clad plate and a circuit board with an authorization publication number of CN 109337072B. However, although the invention introduces an ester structure (C ═ CO) and a bulky group into the structure to make the structure not easy to rotate, and the structure becomes compact after stacking to lower DK and DF, the processing difficulty and production cost are greatly increased with the increase of the glass transition Temperature (TG) and the decrease of the adhesion force, because the heating temperature required for processing must exceed 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 30 wt.% and a viscosity of 20000-50000 CPS.
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 consisting ofSupplied by Thailand science and technology, model number is AD6, and molecular formula is (C)60H69O6N2) n, molecular weight 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 the following specific structure:
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 12-18 um.
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 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 the temperature of 200-300 ℃ to obtain the double-sided high-frequency copper-clad plate;
the baking conditions are as follows: keeping the temperature at 140 ℃ for 15 min;
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-92F-HA-V2, model GHY5, model GS01, model FL-93F-HA-V2, and model GS01, model seiko technologies ltd.
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 improved, and the DK and DF values are effectively reduced by introducing C-OO structure, so that the electrical 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 is selected to be randomly copolymerized with aromatic tetracarboxylic dianhydride and aromatic diamine with a C-OO structure 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 the DK and the DF value, 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-trimellitic acid ester dianhydride, known by the english name p-phenylenebis (trimetallitene anhydride), abbreviated as TAHQ, and having CAS number 2770-49-2;
bisphenol A type diether dianhydride, known by the English name 4,4'- (4,4' -isopropylidenephenoxy) bis (phthalic), abbreviated as BPADA and having CAS number 38103-06-9.
The long-chain dianhydride used in the examples of the present invention is exemplified by, but not limited to, the following:
modified polyimide, available from Solvent soluble thermoplastic polyimide resins and polymers derived from raw materials, type AD6, molecular formula (C)60H69O6N2) n, molecular weight 33000-46000, from Tacostas science, having the following physical parameters:
TABLE 1
The aromatic diamines in the examples of the present invention are exemplified by, but not limited to, the following:
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, namely N-methyl-2-pyrrolidone, abbreviated as NMP, and has a CAS number of 872-50-4, but not limited by the number;
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 20000-50000CPS, wherein 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 proportion shown in Table 2, stirring until the NMP and the BPBT 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 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 and reacting for 12 hours, and stirring and dissolving 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, stirring until the NMP and the ODA are dissolved, adding BPADA and AD6, stirring and reacting for 12 hours, and stirring and 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 and reacting for 12 hours, and stirring and dissolving to obtain the low-TG high-frequency MPI composition.
Example 6
Adding NMP and BPBT into a 500mL reaction bottle according to the mixture ratio shown in the table 3 respectively, stirring until the NMP and the BPBT are dissolved, adding TAHQ and AD6, stirring and reacting for 12 hours, and stirring and 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 and reacting for 12 hours, and stirring and dissolving 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 (Nihonie mine Metal 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 obtaining the double-sided high-frequency copper-clad plate through hot-pressing (at the temperature of 200-; wherein the baking conditions are as follows: keeping the temperature at 140 ℃ for 15 min; 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 12-18 um.
Preparation of double-sided high-frequency copper-clad plate of comparative example 1-2
As shown in FIG. 4, two identical copper foils were used, the copper foil type being BHM-102F-HA-V2, and the thickness being 12um (Nihon Nigri metals Co., Ltd.); coating the high-frequency MPI composition of comparative example 1 or 2 on one side of one 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 15 min; 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 12-18 um.
Preparation of double-sided high-frequency copper-clad plate of comparative example 3
Two identical copper foils were taken, the copper foils were of type BHM-102F-HA-V2 and were 12um thick (from Nissan mine Metal Co., Ltd.); a commercial high-frequency MPI film (purchased from Kaneka company, model number SR # SW, thickness 25um) is stacked between two copper foils, and the double-sided high-frequency copper clad laminate is obtained through hot-pressing (temperature 300-.
Preparation of double-sided high-frequency copper-clad plate of comparative example 4
Two identical copper foils were taken, the copper foils were of type BHM-102F-HA-V2 and were 12um thick (from Nissan mine Metal Co., Ltd.); a commercially available LCP film (purchased from Kuraray company, model CT-Q, thickness 25um) is stacked between two copper foils, and the double-sided high-frequency copper-clad plate is obtained through hot-pressing (temperature of 300-.
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 6502.5.5.13;
(2) and (3) testing conditions are as follows: sample size: 7cm (width) × 12cm (length); 10 GHz;
2. glass transition Temperature (TG) test
(1) And (4) testing standard: IPC-TM 6502.4.24.5 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 6502.4.9 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-TM6502.4.13;
(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 the 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 which can improve the peel strength and maintain the electrical property when a copper clad laminate is prepared, as also confirmed by the test results of example 5 and comparative example 2 in table 3.
In addition, as can be seen from the test results of examples 1 to 4 and examples 5 to 8, example 5 is the best example, and the aromatic tetracarboxylic dianhydride selected in example 5 is TAHQ and the aromatic diamine ABHQ both have a C ═ OO structure, so that the structures can be stacked tightly, the values of DK and DF can be effectively reduced, and when the structure is matched with the long-chain dianhydride AD6, the peeling strength can be greatly improved and the electrical property can be maintained when TG is reduced.
The foregoing shows and describes the general principles, essential 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 (8)
1. A low-TG high-frequency MPI composition is characterized by being prepared from the following components in parts by weight:
the low-TG high-frequency MPI composition has a solids content of 30 wt.% and a viscosity of 20000-50000 CPS.
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-ditrimellitanyl dianhydride and bisphenol A type diether dianhydride.
3. The low-TG, high-frequency MPI composition as in claim 1, wherein the long-chain dianhydride is a modified polyimide having the formula (C)60H69O6N2) n, molecular weight 33000-46000.
4. 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.
5. The low-TG, high-frequency MPI composition according to claim 1, wherein the solvent is one of N-methylpyrrolidone, N-dimethylacetamide and butyrolactone.
6. A double-sided high-frequency copper-clad plate prepared from the low-TG high-frequency MPI composition as claimed in any one of claims 1 to 5, which comprises copper foils on two sides and a high-frequency MPI layer arranged between the copper foils on 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 high frequency MPI layer is 12-25um, and the thickness of copper foil is 12-18 um.
7. A method for preparing a double-sided high-frequency copper-clad plate prepared from the low-TG high-frequency MPI composition of claim 6, comprising 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 the temperature of 200-300 ℃ to obtain the double-sided high-frequency copper-clad plate;
the baking conditions are as follows: keeping the temperature at 140 ℃ for 15 min;
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.
8. The method for preparing a double-sided high-frequency copper-clad plate prepared from the low-TG high-frequency MPI composition according to claim 7, wherein the copper foil is one of electrolytic copper with model TQ-M4-VSP of Nippon Mitsui Metal mining corporation, electrolytic copper with model CF-T49A-DS-HD2 of Nippon Futian Metal foil powder Industrial Co., Ltd, electrolytic copper with model JXEFL-BHM of Nippon Nikko Metal Co., Ltd, electrolytic copper with model FL451 of Jinju developed copper foil Co., Ltd, copper calendering with model BHFX-92F-HA-V2 of Nippon Nikko Metal Co., Ltd, calendered copper with model GHY5-93F-HA-V2 of Nippon Nikko Metal Co., Ltd, and copper with model GS01 of Taixin technology Co., Ltd.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010468663.1A CN111533906B (en) | 2020-05-28 | 2020-05-28 | Low-TG high-frequency MPI composition and double-sided high-frequency copper-clad plate thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010468663.1A CN111533906B (en) | 2020-05-28 | 2020-05-28 | Low-TG high-frequency MPI composition and double-sided high-frequency copper-clad plate thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111533906A true CN111533906A (en) | 2020-08-14 |
| CN111533906B CN111533906B (en) | 2023-04-07 |
Family
ID=71972383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010468663.1A Active CN111533906B (en) | 2020-05-28 | 2020-05-28 | Low-TG high-frequency MPI composition and double-sided high-frequency copper-clad plate thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111533906B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08294993A (en) * | 1995-04-27 | 1996-11-12 | Kanegafuchi Chem Ind Co Ltd | Flexible copper plated laminate board |
| US20080035575A1 (en) * | 2006-08-08 | 2008-02-14 | Partridge Randall D | Polymer membrane for separating aromatic and aliphatic compounds |
| 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 |
| CN109808259A (en) * | 2019-02-02 | 2019-05-28 | 江阴骏驰复合材料有限公司 | A kind of high frequency double face copper and the preparation method and application thereof |
| CN111073284A (en) * | 2019-12-18 | 2020-04-28 | 武汉华星光电半导体显示技术有限公司 | Polyimide film, preparation method thereof and display device |
-
2020
- 2020-05-28 CN CN202010468663.1A patent/CN111533906B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08294993A (en) * | 1995-04-27 | 1996-11-12 | Kanegafuchi Chem Ind Co Ltd | Flexible copper plated laminate board |
| US20080035575A1 (en) * | 2006-08-08 | 2008-02-14 | Partridge Randall D | Polymer membrane for separating aromatic and aliphatic compounds |
| 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 |
| CN109808259A (en) * | 2019-02-02 | 2019-05-28 | 江阴骏驰复合材料有限公司 | A kind of high frequency double face copper and the preparation method and application thereof |
| CN111073284A (en) * | 2019-12-18 | 2020-04-28 | 武汉华星光电半导体显示技术有限公司 | Polyimide film, preparation method thereof and display device |
Non-Patent Citations (1)
| Title |
|---|
| 朱美芳 周哲: "《中国战略性新兴产业——新材料 高性能纤维》", 30 November 2017, 中国铁道出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111533906B (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101740802B1 (en) | Polyimide resin, thin film and method for manufacturing thereof | |
| CN110204718B (en) | Polyimide film, preparation method thereof and copper-clad plate | |
| CN106335249B (en) | Metal laminate plate comprising polyimide resin and method for producing same | |
| CN109337072B (en) | Low DK and DF polymer composition, copper-clad plate and circuit board | |
| CN109203602B (en) | High-frequency double-sided copper-clad plate and preparation method and application thereof | |
| CN113563585B (en) | Polyimide and application thereof in metal laminated plate | |
| CN110744891A (en) | Blending modified polyimide high-frequency adhesive-free flexible copper clad laminate and manufacturing method thereof | |
| CN113308091B (en) | Liquid crystal polyester resin composition and application thereof | |
| Tasaki et al. | Low transmission loss flexible substrates using low Dk/Df polyimide adhesives | |
| CN104441831A (en) | Low-dielectric-constant two-side flexible copper-clad plate of novel structure | |
| CN111533906B (en) | Low-TG high-frequency MPI composition and double-sided high-frequency copper-clad plate thereof | |
| CN110744890A (en) | Fluorine polyimide high-frequency adhesive-free flexible copper clad laminate and manufacturing method thereof | |
| CN102848642B (en) | Two layers of method double side flexible copper coated board and preparation method thereof | |
| CN111479395B (en) | Preparation method of glue-free flexible copper-clad plate | |
| CN106800908B (en) | Thermoplastic polyimide adhesive for two-layer flexible copper clad laminate and preparation method and application thereof | |
| CN111484616B (en) | Polyimide composition, polyimide, flexible copper clad laminate and manufacturing method thereof | |
| TWI748769B (en) | Polymer dispersion, method for manufacturing the polymer dispersion, and polymer composite film and its application | |
| JP2927531B2 (en) | Flexible printed circuit board and method of manufacturing the same | |
| KR102491338B1 (en) | flexible metal clad laminate and THERMOPLASTIC POLYIMIDE PRECORSOR COMPOSITION for flexible metal clad laminate | |
| CN107916090B (en) | Low-modulus high-bonding-capacity thermoplastic polyimide composition and application and preparation method thereof | |
| CN112373150A (en) | Preparation method of glue-free single-sided flexible copper-clad plate based on coating method | |
| CN111662640A (en) | Modified liquid crystal material for 5G communication, copper-clad plate and preparation method thereof | |
| CN111559135A (en) | Polyimide lamination, preparation method thereof and copper-clad plate comprising polyimide lamination | |
| CN112822835B (en) | Polyimide copper-clad substrate | |
| Tasaki | Low transmission loss polyimides substrates: a novel alternative to liquid crystal polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |