CN109337072B

CN109337072B - Low DK and DF polymer composition, copper-clad plate and circuit board

Info

Publication number: CN109337072B
Application number: CN201811124425.8A
Authority: CN
Inventors: 周立
Original assignee: Jiangyin Junchi New Material Technology Co Ltd
Current assignee: Jiangyin Junchi New Material Technology Co Ltd
Priority date: 2018-09-26
Filing date: 2018-09-26
Publication date: 2020-05-19
Anticipated expiration: 2038-09-26
Also published as: CN109337072A

Abstract

The invention discloses a low DK and DF polymer composition, which is prepared from the following components in parts by weight: 20-60 parts of dianhydride containing ester groups, 1-25 parts of diamine monomer containing pyrimidine groups and 100-180 parts of solvent. The invention also discloses a copper-clad plate prepared from the polymer composition with low DK and DF, which comprises a copper foil and a polyimide layer attached to the surface of the copper foil, wherein the polyimide layer is formed by coating the polymer composition with low DK and DF on the surface of the copper foil and heating and cyclizing at high temperature. The polymer composition with low DK and DF solves the problem of overhigh DK and DF, provides a laminated body for a circuit board with a polyimide layer, and can obtain the characteristics of low DK and DF and high transmission when the polyimide layer is matched with a copper foil with low roughness.

Description

Low DK and DF polymer composition, copper-clad plate and circuit board

Technical Field

The invention belongs to the technical field of electronic materials, and particularly relates to a low DK and DF polymer composition, a copper-clad plate and a circuit board.

Background

At present, the industry technology of PCB is developed to a method of high frequency, high speed and high density packaging regardless of the soft board and the hard board, corresponding to the development trend of light, thin, portable and multi-functional products, the demand for materials and preparation methods will become more and more severe, and the development trend of high frequency band (-GHZ) is a study in addition to the rapid development of data transmission brought by the resource/communication action, wherein the most important material characteristic demand is LOW DK/DF and high heat resistance and peeling strength.

The trend of light weight, thinness, portability and multi-functionalization is more and more demanding on materials and preparation methods, and the trend of data transmission is rapidly developed by adding to the data/communication mobility, and the trend of high frequency band (GHZ) is a remarkable study, wherein the most important material characteristic requirements are LOW DK/DF and high heat resistance and peeling strength.

In the prior art, diamine and dianhydride are generally synthesized into polyamide acid (PAA), and the polyamide acid (PAA) is synthesized into Polyimide (PI) through a dehydration reaction by a high-temperature cyclization method. However, Dk is 3.0 or more due to high Moore polarizability of atomic groups, and Df is 0.008 or more due to loose structural arrangement, so that Dk and Df need to be introduced into molecular structures and stacked structurally, as shown below.

Disclosure of Invention

In order to solve the problem of too high DK and DF, it is a first object of the present invention to provide a polymer composition with low DK and DF.

The invention also aims to provide a copper-clad plate prepared from the polymer composition with low DK and DF.

The invention further aims to provide a circuit board made of the copper-clad plate.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the invention provides a low DK and DF polymer composition, which is prepared from the following components in parts by weight:

20-60 parts of dianhydride containing ester groups;

1-25 parts of a diamine monomer containing a pyrimidine group;

100-180 parts of a solvent.

The dianhydride containing the ester group is aromatic tetracarboxylic dianhydride, preferably p-phenylene-ditrimellic dianhydride (TAHQ), 3',4,4' -biphenyl tetracarboxylic dianhydride (BPDA) and bisphenol A diether dianhydride (BPADA), and has the following specific structure:

the diamine monomer containing pyrimidine groups is aromatic diamine, preferably 3, 5-diamino-1, 2,4-triazole (DTZ), 1,4-phenylene bis (4-Aminobenzoate) (ABHQ), terephthalic acid di-p-aminophenyl ester (BPTP), p-aminobenzoic acid p-aminophenyl ester (APAB), 4' -diaminodiphenyl ether (ODA) and bis (4-aminophenyl) terephthalate (BPBT), and has the following specific structure:

the diamine monomer containing pyrimidine group is a mixture of 3, 5-diamino-1, 2,4-triazole (DTZ), p-aminobenzoic acid p-aminophenyl ester (APAB) and 4,4' -diaminodiphenyl ether (ODA).

The solvent is N-methyl pyrrolidone (NMP), N-dimethyl acetamide, butyrolactone, N-dimethyl formamide and dimethyl sulfoxide.

The solid content of the low DK and DF polymer composition is 30 wt% (low DK and DF polyamic acid solution), and the viscosity is 30000-60000 CPs.

A second aspect of the invention provides a method of preparing the low DK and DF polymeric composition, comprising the steps of:

and dissolving dianhydride containing ester groups and diamine monomer containing pyrimidine groups in a solvent according to the proportion, and stirring and dissolving to obtain the low DK and DF polymer composition.

The invention also provides a copper-clad plate prepared from the polymer composition with low DK and DF, which comprises a copper foil and a polyimide layer attached to the surface of the copper foil, wherein the polyimide layer is formed by coating the polymer composition with low DK and DF on the surface of the copper foil and heating and cyclizing at high temperature.

The thickness of the polyimide layer is 9-50 um.

The thickness of the copper foil is 12-18 um.

The fourth aspect of the invention provides a preparation method of a copper-clad plate prepared from the polymer composition with low DK and DF, which comprises the following steps:

and (3) coating the high polymer composition with low DK and DF on a copper foil through a coating process, and baking and curing to form a polyimide layer with low DK and DF so as to obtain the copper-clad plate.

The copper foil model is BHFX-92F-HA-V2-12 μm, and RZ is 0.45 (Riyaite).

The baking condition is 140 ℃, the temperature is kept for 15min, and then the temperature is reduced to the room temperature.

The curing condition is that the temperature is raised to 150 ℃ after 15min at room temperature, the temperature is kept for 5min, the temperature is raised to 200 ℃ after 10min, the temperature is kept for 5min, the temperature is raised to 250 ℃ after 10min, the temperature is kept for 5min, the temperature is raised to 300 ℃ after 10min, the temperature is kept for 30min, the temperature is raised to 350 ℃ after 10min, the temperature is kept for 30min, and then the temperature is lowered to room temperature after 60 min.

The principle of the invention is partly as follows:

the method for reducing the dielectric constant comprises the following steps:

Claslius-Mosotti equation:

wherein Pm is the Moore polarizability of the atomic group, and Vm is the Moore volume of the atomic group.

Pm can be reduced by introducing an ester functional group, and Vm can be increased by introducing a large group to destroy the coplanar of benzene rings. Therefore, the method for reducing the dielectric constant mainly comprises introducing ester functional groups, closely arranging the structure, and blending the low Df material.

General PI is soft (CH) due to its structure₂O-, etc.) and thus stacking is not tight, and Dk and Df are not increased, so that the structure is not easy to rotate due to introduction of an ester structure (C ═ CO) and introduction of a bulky group, and Dk and Df are decreased due to tight stacking.

The prior art stack gap is as follows:

Dk＝3.2

Df＝0.008。

the stack of this application is closely, specifically as follows:

for the conductor copper foil, the smoother the conductor surface, the shorter the current flow path, and the rougher the conductor surface, the longer the current flow path, as shown in fig. 1, fig. 1 is a schematic view of the conductor copper foil surface when current flows. The copper foil having LOW roughness may be selected to have excellent LOW DK and DF characteristics, but when the copper foil has LOW roughness, it causes a defect of LOW adhesion between the polyimide layer and the copper foil. Therefore, the molecular structure design of the composition can improve the adhesion strength to copper. The composition uses diamine monomer containing pyrimidine group, wherein the coordination of the pyrimidine group and copper enhances the bonding strength of polyimide and copper foil. As shown in fig. 2, fig. 2 is a schematic view of a prior art material attached to a copper foil. The peel strength in the prior art is 0.5kgf/cm, the present application coordinates with copper, and the peel strength is 0.9 kgf/cm.

The fifth aspect of the invention provides a circuit board made of the copper-clad plate.

Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:

the polymer composition with low DK and DF solves the problem of overhigh DK and DF, provides a laminated body for a circuit board with a polyimide layer, can be made into the laminated body for the circuit board after a copper-clad plate is made, and can obtain the characteristics of low DK, low DF and high transmission when the polyimide layer is matched with a copper foil with low roughness.

The polyamic acid solution, which is a polymer composition having a low DK and DF, of the present invention is a composition that can reduce DK and DF and has excellent heat resistance. The composition uses dianhydride containing ester groups and diamine monomers containing pyrimidine groups, wherein the matching effect of LOW DK & DF glue and copper can be effectively prepared into high frequency. The composition has the solid content of 30 percent and the viscosity of 30000-60000CPs, can be coated on a copper foil through a coating process, and is imidized through heating treatment to form an LOW DK and DF polyimide polymer, wherein the LOW DK and DF polyimide polymer can generate heat-resistant LOW DK and DF polyimide layers on the surface of the copper foil, and the heat-resistant LOW DK and DF polyimide layers are products such as a high-frequency adhesive-free flexible circuit board base material (2L-FCCL). Flexible copper foil substrates (FCCL) are divided into two main categories: the traditional three-layer soft board base material (3L FCCL) with an adhesive agent type and the novel two-layer soft board base material (2L FCCL) without the adhesive agent type are two main types. The present application pertains to a two-layer flexible board substrate (2L FCCL) without an adhesive.

Generally, the tension of a high-frequency copper foil copper-clad plate is 0.5-0.7kgf/cm, and 3, 5-diamino-1, 2,4-triazole DTZ is added to improve the tension; the electrical property of general copper foil copper-clad plate is on the high side (DF is 0.008), adds C in this application and OO structure can effectively reduce DF (DF is 0.003), consequently, this application adds DTZ and introduces C and OO structure can promote the pulling force simultaneously and reduce DF.

Drawings

FIG. 1 is a schematic view showing a surface current of a conductor copper foil flowing therethrough.

Fig. 2 is a schematic illustration of a prior art and present application material attached to a copper foil.

FIG. 3 is a flow chart of the preparation process of the copper-clad plate of the invention.

FIG. 4 is a schematic view of the aging conditions.

FIG. 5 is a flow chart of a process for preparing a copper-clad plate according to an embodiment of the invention.

FIG. 6 is a flow chart of a process for preparing a copper-clad plate of a comparative example.

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 reagents used in the examples of the invention were as follows:

diamine (b): the diamine monomer in the invention can be aromatic diamine, and can be the following monomers, but is not limited to the monomers; chinese: 3, 5-diamino-1, 2,4-triazole, english: 1,2, 4-Triazo-3, 5-diamine, abbreviation: DTZ, CAS: 1455-77-2. Chinese: 1, 4-phenylenebis (4-aminobenzoate), english: 1,4-phenylene Bis (4-aminobenzoate) or 1,4-Bis (4-aminobenzoxy) bezene, abbreviation: ABHQ, CAS: 22095-98-3. Chinese: di-p-aminophenyl terephthalate, english: bis (4-aminophenyl) tert-plate, abbreviation: BPTP, CAS: 16926-73-1. Chinese: p-aminobenzoate, english: 4-Aminophenyl-4-aminobenzoate, abbreviation: APAB, CAS: 20610-77-9. Chinese: 4,4' -diaminodiphenyl ether, english: 4,4' -oxybisbenzenamine, abbreviation: and (4) ODA. Chinese: bis (4-aminophenyl) terephthalate, english: bis (4-aminophenyl) tert-plate, abbreviation: BPBT.

Dianhydride: the dianhydride monomer in the present invention can be aromatic tetracarboxylic dianhydride, and is exemplified by the following, but not limited thereto; chinese: p-phenylene-ditrimellitic dianhydride, english: p-phenylenebis (trimetalliteneanhydride), abbreviation: TAHQ, CAS: 2770-49-2. Chinese: 3,3',4,4' -biphenyltetracarboxylic dianhydride, english: 3,3',4,4' -biphenylquaternary dianhydrides, abbreviation: BPDA, CAS: 2420-87-3. Chinese: bisphenol a type diether dianhydride, english: 4,4'- (4,4' -ISOPROPYLIDENEDIPHENOXY) BIS (PHTHALIC ANHYDRIDE), abbreviation: BPADA, CAS: 38103-06-9.

Examples 1 to 4

The raw materials used in examples 1-4 are shown in table 1, and a method for preparing the polymer composition with low DK and DF comprises the following steps: and (3) stirring NMP, APAB, ODA and DTZ at a high speed until the NMP, the APAB, the ODA and the DTZ are dissolved, adding BPDA, and stirring for reaction for 12 hours to obtain the low DK and DF polymer composition.

A preparation method of a copper-clad plate prepared from the low DK and DF polymer composition comprises the following steps:

the polymer composition with low DK and DF is coated on a copper foil (the copper foil is Cu: BHFX-92F-HA-V2-12 μm, RZ ═ 0.45 (ri mine)) through a coating process, and a polyimide layer with low DK and DF is formed through baking and curing to obtain the copper-clad plate, specifically as shown in fig. 3 and fig. 5, fig. 3 is a flow chart of a preparation process of the copper-clad plate of the present invention, and fig. 5 is a flow chart of a preparation process of the copper-clad plate of the embodiment of the present invention.

The baking condition is 140 ℃, the temperature is kept for 15min, and then the temperature is reduced to the room temperature; the curing condition (specifically as shown in fig. 4, fig. 4 is a schematic view of the curing condition) is that the temperature is raised to 150 ℃ for 15min, the temperature is kept for 5min, the temperature is raised to 200 ℃ for 10min, the temperature is kept for 5min, the temperature is raised to 250 ℃ for 10min, the temperature is kept for 5min, the temperature is raised to 300 ℃ for 10min, the temperature is kept for 30min, the temperature is raised to 350 ℃ for 10min, the temperature is kept for 30min, and then the temperature is reduced to room temperature for 60 min.

The copper-clad plate comprises a copper foil and a polyimide layer attached to the surface of the copper foil, wherein the polyimide layer is formed by coating the low DK and DF polymer composition on the surface of the copper foil and heating and cyclizing at high temperature. The thickness of polyimide layer is 9-50um, the thickness of copper foil is 12-18 um. And testing DK and DF on the prepared copper-clad plate, then testing the peel strength, and finally carrying out a floating tin test, wherein the floating tin test lasts for 10sec at the temperature of 340 ℃, and the test shows that the copper-clad plate passes. According to the test results in table 1, the copper-clad plate of the present invention has better performance than the comparative example.

TABLE 1

30% of solid and 30000-60000 CPs.

The amount of diamine used was 21.21g in total in example 1, 21.49g in total in example 2, 21.76g in total in example 3 and 22.04g in total in example 4.

Examples 5 to 8

The raw materials used in examples 5-8 are shown in table 2, and a method for preparing the polymer composition with low DK and DF comprises the following steps: and (3) stirring NMP, APAB, ODA and DTZ at a high speed until the NMP, APAB, ODA and DTZ are dissolved, adding BPADA, and stirring for reaction for 12 hours to obtain the low DK and DF polymer composition.

coating the high polymer composition of the low DK and the DF on a copper foil (the copper foil is Cu: BHFX-92F-HA-V2-12 mu m, RZ is 0.45 (Riyaite)) through a coating process, and baking and curing to form a polyimide layer of the low DK and the DF so as to obtain a copper-clad plate; the baking condition is 140 ℃, the temperature is kept for 15min, and then the temperature is reduced to the room temperature; the curing condition is that the temperature is raised to 150 ℃ after 15min at room temperature, the temperature is kept for 5min, the temperature is raised to 200 ℃ after 10min, the temperature is kept for 5min, the temperature is raised to 250 ℃ after 10min, the temperature is kept for 5min, the temperature is raised to 300 ℃ after 10min, the temperature is kept for 30min, the temperature is raised to 350 ℃ after 10min, the temperature is kept for 30min, and then the temperature is lowered to room temperature after 60 min.

The copper-clad plate comprises a copper foil and a polyimide layer attached to the surface of the copper foil, wherein the polyimide layer is formed by coating the low DK and DF polymer composition on the surface of the copper foil and heating and cyclizing at high temperature. The thickness of polyimide layer is 9-50um, the thickness of copper foil is 12-18 um. And testing DK and DF on the prepared copper-clad plate, then testing the peel strength, and finally carrying out a floating tin test. According to the test results in table 2, it can be shown that the copper-clad plate of the present invention has better performance than the comparative example.

TABLE 2

Solid fraction 30% viscosity 30000-60000 CPs.

The amount of diamine used was 21.21g in total in example 5, 21.49g in total in example 6, 21.76g in total in example 7 and 22.04g in total in example 8.

Examples 9 to 12

The raw materials used in examples 9-12 are shown in table 3, and a method for preparing the polymer composition with low DK and DF comprises the following steps: and (3) stirring NMP, APAB, ODA and DTZ at a high speed until the NMP, the APAB, the ODA and the DTZ are dissolved, adding TAHQ, and stirring for reacting for 12 hours to obtain the low DK and DF polymer composition.

The copper-clad plate comprises a copper foil and a polyimide layer attached to the surface of the copper foil, wherein the polyimide layer is formed by coating the low DK and DF polymer composition on the surface of the copper foil and heating and cyclizing at high temperature. The thickness of polyimide layer is 9-50um, the thickness of copper foil is 12-18 um. And testing DK and DF on the prepared copper-clad plate, then testing the peel strength, and finally carrying out a floating tin test. According to the test results in table 3, it can be shown that the copper-clad plate of the present invention has better performance than the comparative example.

TABLE 3

Solid fractions 30% viscosity 30000-60000 CPs.

The total amount of diamine used was 21.21g in example 9, 21.49g in example 10, 21.76g in example 11 and 22.04g in example 12.

Comparative examples 1 and 2

Specific examples of comparative examples 1 and 2 are shown in table 4 and fig. 6. FIG. 6 is a flow chart of a process for preparing a copper-clad plate of a comparative example. Coating Liquid Crystal Polymer (LCP) on a copper foil, baking for 20min at the temperature of 90 ℃, and annealing for 180min at the temperature of 300 ℃ to obtain the product.

TABLE 4

	Comparative example 1	Comparative example 2
			Manufacturer(s)	Taiflex (2LP) in general	Azotek (LDS) high frequency
Model number	2LP	LDS
			DK(10GHz)	3.2	2.8
DF(10GHz)	0.008	0.004
			Peel Strength (Kgf/cm)	0.85	0.55
Tin bleaching test	320℃10sec PASS	340℃10sec PASS

The copper-clad plates prepared in the embodiments 1 to 12 are made into circuit boards.

Comparative examples 3 to 5

The raw materials used in comparative examples 3 to 5 are shown in tables 1 to 3, and include the following steps: and (3) stirring NMP, PDA and ODA at a high speed according to the proportion in the table 1-3 until the NMP, the PDA and the ODA are dissolved, adding dianhydride BPDA or BPADA or TAHQ, and stirring for reacting for 12 hours to obtain the polymer composition.

The preparation method of the copper-clad plate prepared from the polymer composition comprises the following steps:

coating the polymer composition on a copper foil (the copper foil is Cu: BHFX-92F-HA-V2-12 μm, RZ is 0.45 (Nissan)), baking and curing to form a polyimide layer, thereby obtaining a copper-clad plate; the baking condition is 140 ℃, the temperature is kept for 15min, and then the temperature is reduced to the room temperature; the curing condition is that the temperature is raised to 150 ℃ after 15min at room temperature, the temperature is kept for 5min, the temperature is raised to 200 ℃ after 10min, the temperature is kept for 5min, the temperature is raised to 250 ℃ after 10min, the temperature is kept for 5min, the temperature is raised to 300 ℃ after 10min, the temperature is kept for 30min, the temperature is raised to 350 ℃ after 10min, the temperature is kept for 30min, and then the temperature is lowered to room temperature after 60 min.

The copper-clad plate comprises a copper foil and a polyimide layer attached to the surface of the copper foil, wherein the polyimide layer is formed by coating the polymer composition on the surface of the copper foil and heating and cyclizing at high temperature. The thickness of polyimide layer is 9-50um, the thickness of copper foil is 12-18 um. And testing DK and DF on the prepared copper-clad plate, then testing the peel strength, and finally carrying out a floating tin test.

According to the copper-clad plate prepared by using ODA + DTZ + APAB as the diamine in the embodiments 1-4, ODA + PDA as the diamine in the comparative example 3 and the same other components, through performance tests, the DK in the embodiments 1-4 is respectively 2.89, 2.86 and 2.82, the DK in the comparative example 3 is 3.2, and the DK value in the embodiments is reduced compared with that in the comparative example; in examples 1 to 4, DF was 0.0038, 0.0036, 0.0035, and 0.0035, respectively, and in comparative example 3, DF was 0.008, and it was found that the DK value was lower in the examples than in the comparative examples; in summary, DK and DF can be effectively reduced by selecting the diamine used in the embodiments of the present invention.

In examples 5 to 8, the diamine is ODA + DTZ + APAB, in comparative example 4, the diamine is ODA + PDA, and the other components are the same, and performance tests show that the prepared copper-clad plate has DK of 2.89, 2.86 and 2.82 in examples 5 to 8 and DK of 3.1 in comparative example 4, and the DK value of the examples is reduced compared with that of the comparative example; in examples 5 to 8, DF was 0.0038, 0.0036, 0.0035, and 0.0035, respectively, and in comparative example 4, DF was 0.008, and it was found that the DK value was lower in the examples than in the comparative examples; in summary, DK and DF can be effectively reduced by selecting the diamine used in the embodiments of the present invention.

In examples 9 to 12, the diamine is ODA + DTZ + APAB, in comparative example 5, the diamine is ODA + PDA, and the other components are the same, and performance tests show that the prepared copper-clad plate has DK values of 3.14, 3.18, 3.23 and 3.27 in examples 9 to 12 and DK of 3.3 in comparative example 5, and the DK values of the examples are reduced compared with the comparative example; in examples 9 to 12, DF was 0.0034, 0.0028, and 0.0022, respectively, and in comparative example 5, DF was 0.006, and it was found that DK value was lower in examples than comparative examples; in summary, DK and DF can be effectively reduced by selecting the diamine used in the embodiments of the present invention.

In summary, in the examples of the present invention, APAB is introduced, and the addition of C ═ OO functional group to the structure can effectively reduce DF (by about 1/2), and the tensile force of the comparative examples is reduced compared to the tensile force of the examples, so DTZ is added to raise the tensile force.

Comparative examples 6 to 8

The raw materials used in comparative examples 6 to 8 are shown in table 5, and include the following steps: NMP, PDA, ODA and DTZ are stirred at a high speed according to the proportion in the table 5 until the NMP, PDA, ODA and DTZ are dissolved, then dianhydride BPDA or BPADA or TAHQ is added, and stirring reaction is carried out for 12 hours, so as to obtain the polymer composition.

The preparation method for preparing the copper-clad plate from the polymer composition comprises the following steps:

TABLE 5

Examples 13 to 15

The raw materials used in examples 13-15 are shown in table 6, and a method for preparing the polymer composition with low DK and DF comprises the following steps: and (3) adding dianhydride to the mixture of NMP, APAB, ODA and DTZ according to the proportion in the table 6 after stirring at a high speed until the mixture is dissolved, and stirring for reaction for 12 hours to obtain the low DK and DF polymer composition.

The copper-clad plate comprises a copper foil and a polyimide layer attached to the surface of the copper foil, wherein the polyimide layer is formed by coating the low DK and DF polymer composition on the surface of the copper foil and heating and cyclizing at high temperature. The thickness of polyimide layer is 9-50um, the thickness of copper foil is 12-18 um. And testing DK and DF on the prepared copper-clad plate, then testing the peel strength, and finally carrying out a floating tin test. According to the test results in table 6, it can be shown that the copper-clad plate of the present invention has better performance than the comparative example.

TABLE 6

According to performance tests, the copper-clad plate prepared by using ODA + DTZ + APAB as the diamine in example 13, ODA + DTZ + PDA as the diamine in comparative example 6 and the other components as the diamine in the comparative example 6 has DK of 3.2 in example 13 and DK of 3 in comparative example 6, and the fact that the diamine APAB in example 13 is changed into PDA in comparative example 6 and the other diamines are not changed results in higher DK values in the examples than the comparative examples; the DF was 0.0043 in example 13 and 0.01 in comparative example 6, and it was found that the DF was lower in the examples than in the comparative example when the diamine APAB in example 13 was changed to PDA in comparative example 6 and the other diamines were not changed; in summary, the diamine used in the embodiment of the present invention can effectively reduce DF and increase DK value. It can also be seen from tables 5 and 6 that the thermogravimetric loss temperature of the examples is improved (the heat resistance is increased) compared to the comparative examples.

In the embodiment 14, the diamine is ODA + DTZ + APAB, in the comparative example 7, the diamine is ODA + DTZ + PDA, and the other components are the same, the performance test of the prepared copper-clad plate shows that the DK in the embodiment 14 is 3.2, the DK in the comparative example 7 is 3.1, the diamine APAB in the embodiment 14 is changed into the PDA in the comparative example 7, and the other diamines are not changed, so that the DK value of the embodiment is increased compared with that of the comparative example; the DF for example 14 was 0.0044 and the DF for comparative example 7 was 0.009. it was found that the substitution of the diamine APAB for the PDA in comparative example 7 in example 14, with the other diamines unchanged, reduced the DF values for the examples compared to the comparative examples; in summary, the diamine used in the embodiment of the present invention can effectively reduce DF and increase DK value. It can also be seen from tables 5 and 6 that the thermogravimetric loss temperature of the examples is improved (the heat resistance is increased) compared to the comparative examples.

In the embodiment 15, the diamine is ODA + DTZ + APAB, in the comparative example 8, the diamine is ODA + DTZ + PDA, and the other components are the same, the performance test of the prepared copper-clad plate shows that the DK in the embodiment 15 is 3.4, the DK in the comparative example 8 is 3.2, the diamine APAB in the embodiment 15 is changed into the PDA in the comparative example 8, and the other diamines are not changed, so that the DK value in the embodiment is increased compared with that in the comparative example; the DF was 0.0035 for example 15 and 0.007 for comparative example 8, it was found that the DF was lower for the examples than for the comparative example when the diamine APAB of example 15 was changed to PDA of comparative example 8 and the other diamines were not changed; in summary, the diamine used in the embodiment of the present invention can effectively reduce DF and increase DK value.

In summary, the PDA in the comparative example was replaced with APAB, and the value of DF was effectively reduced by introducing a C — OO structure. In the embodiment of the invention, the APAB (functional group C ═ OO) is added to enable the structure to be stacked tightly, the value of DF is effectively reduced, and the DF is obviously reduced by half from the comparative example, but because the structure is stacked too tightly, the steel hardness is caused, and the tensile force is reduced (comparative examples 3-5), the DTZ is added to the structure, so that the N in the structure can be coordinated with the copper to improve the tensile force.

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

1. A low DK and DF polymeric composition, comprising: after 118g of NMP, 13.7g of APAB, 7.01g of ODA and 0.5g of DTZ were stirred at a high speed until they were dissolved, 29.4g of BPDA was added thereto and stirred for reaction for 12 hours to obtain the polymer composition with low DK and DF.

2. The low DK and DF polymeric composition of claim 1, wherein: the polymer composition with low DK and DF has the solid content of 30 wt% and the viscosity of 30000-60000 CPs.

3. A copper-clad plate prepared from the polymer composition with low DK and DF of claim 1 or 2, wherein: the polyimide layer is formed by coating the polymer composition with low DK and DF on the surface of the copper foil and heating and cyclizing at high temperature;

the thickness of the polyimide layer is 9-50 um; the thickness of the copper foil is 12-18 um.

4. A method for preparing the copper-clad plate prepared from the low DK and DF polymer composition of claim 3, which is characterized in that: the method comprises the following steps:

coating the high polymer composition with low DK and DF on a copper foil through a coating process, and baking and curing to form a polyimide layer with low DK and DF so as to obtain a copper-clad plate;

5. The method of claim 4, wherein the copper clad laminate is prepared from the polymer composition with low DK and DF, and the method comprises the following steps: the copper foil is BHFX-92F-HA-V2-12 mu m, and RZ is 0.45;

6. A circuit board made from a copper clad laminate prepared from the polymeric composition of low DK and DF of claim 1 or 2.