CN112979948B - Method for producing polyimide precursor and polyimide - Google Patents
Method for producing polyimide precursor and polyimide Download PDFInfo
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- CN112979948B CN112979948B CN202011030363.1A CN202011030363A CN112979948B CN 112979948 B CN112979948 B CN 112979948B CN 202011030363 A CN202011030363 A CN 202011030363A CN 112979948 B CN112979948 B CN 112979948B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- 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
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- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
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- 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
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Abstract
The invention relates to a preparation method of a polyimide precursor and polyimide. The preparation method is to prepare polyimide precursor through a first reaction, a second reaction and a third reaction, wherein the polyimide precursor consists of first polyamic acid, second polyamic acid and third polyamic acid. By using specific tetracarboxylic dianhydride monomer and/or diamine monomer, the prepared polyimide precursor has lower dielectric constant and dielectric loss factor, so as to reduce the insertion loss of the material and increase the transmission rate.
Description
Technical Field
The present invention relates to a polyimide precursor, and more particularly, to a method for preparing a polyimide precursor with low dielectric constant and dielectric dissipation factor, and a polyimide prepared thereby.
Background
With the development of the technology industry, high frequency transmission has been the main transmission means of wireless communication products, so that high frequency substrates with rapid transmission rate are the current development focus. In order to meet the high frequency transmission requirement, the signal loss of the substrate needs to be effectively reduced.
In general, signal loss in a substrate refers to insertion loss (insertion loss) of a signal, and insertion loss is the sum of reflection loss, material loss, and radiation loss. Wherein the material loss includes dielectric loss and conductor loss. Dielectric loss is controlled by the insulating layer, while conductor loss is related to the conductivity and surface roughness of the conductive layer. In addition, the dielectric loss is calculated by the following formula (I), and the formula (I) shows that the dielectric constant and the dielectric loss factor of the material can be reduced effectively, so that the dielectric loss is beneficial to high-frequency transmission.
In formula (I), dk represents the dielectric constant, df represents the dielectric dissipation factor, and f represents the frequency.
In the conventional charge transport substrate, polyimide copper-clad laminate is widely used in electronic products because of its thinness and flexibility. However, the conventional polyimide film has a high dielectric constant and dielectric dissipation factor, so that the application requirements of high-frequency transmission cannot be satisfied.
In view of the foregoing, there is a need to provide a method for preparing polyimide precursor and polyimide, which can improve the defects of the conventional polyimide that the polyimide has too high dielectric constant and dielectric loss factor.
Disclosure of Invention
Therefore, in one aspect of the present invention, a method for preparing a polyimide precursor is provided, wherein a specific tetracarboxylic dianhydride monomer and a diamine monomer are selected for a staged reaction, so as to prepare a block copolymer with regular arrangement, thereby reducing the charge transfer resistance, and meeting the requirement of high-frequency transmission.
In another aspect, the present invention provides a polyimide prepared by heating a polyimide precursor, wherein the polyimide precursor is prepared by the aforementioned method.
According to one aspect of the present invention, a method for fabricating a polyimide precursor is provided. The preparation method comprises the steps of firstly carrying out a first reaction on a first tetracarboxylic dianhydride monomer and a first diamine monomer to form a first polyamic acid. Then, a second reaction is performed on the first polyamic acid, the second tetracarboxylic dianhydride monomer, and the second diamine monomer to form a block polyamic acid. The block polyamic acid is composed of a first polyamic acid and a second polyamic acid, wherein the second polyamic acid is formed from a second tetracarboxylic dianhydride monomer and a second diamine monomer. Next, a third reaction is performed on the blocked polyamic acid, the third tetracarboxylic dianhydride monomer, and the third diamine monomer to form a polyimide precursor. The polyimide precursor is composed of block polyamide acid and third polyamide acid, wherein the third polyamide acid is formed by a third tetracarboxylic dianhydride monomer and a third diamine monomer. One of the first tetracarboxylic dianhydride monomer or the second tetracarboxylic dianhydride monomer may be a tetracarboxylic dianhydride monomer having an ether group in the main chain, and the third diamine monomer may be a diamine monomer having an ether group in the main chain or a diamine monomer having an alkyl group in a side chain.
According to an embodiment of the present invention, the content of the third polyamic acid is 10 to 30 mole percent based on 100 mole percent of the content of the polyimide precursor.
According to another embodiment of the present invention, the content of the first polyamic acid or the second polyamic acid formed by the first tetracarboxylic dianhydride monomer or the second tetracarboxylic dianhydride monomer is 10 to 60 mole percent based on 100 mole percent of the content of the polyimide precursor.
According to yet another embodiment of the present invention, the content of the first polyamic acid or the second polyamic acid formed by the other of the first tetracarboxylic dianhydride monomer or the second tetracarboxylic dianhydride monomer is 20 to 75 mole percent based on 100 mole percent of the content of the polyimide precursor.
According to another embodiment of the present invention, the first diamine monomer and the second diamine monomer are not diamine monomers having ether groups in the main chain or diamine monomers having alkyl groups in the side chains.
According to still another embodiment of the present invention, the aforementioned third tetracarboxylic dianhydride monomer is not a tetracarboxylic dianhydride monomer having an ether group in the main chain.
According to yet another embodiment of the present invention, the total solids content of the aforementioned polyimide precursor is 10 to 25 weight percent.
According to another aspect of the present invention, a polyimide is provided. The polyimide is formed by heating a polyimide precursor, and the polyimide precursor is prepared by the aforementioned manufacturing method. Wherein each molecular chain of polyimide is composed of a first polyamic acid, a second polyamic acid and a third polyamic acid.
According to an embodiment of the invention, the dielectric dissipation factor of the polyimide is 0.003 to 0.005 and the dielectric constant is 3.0 to 3.7.
The preparation method of polyimide precursor and polyimide can utilize specific tetracarboxylic dianhydride monomer and diamine monomer to make sectional reaction so as to form the block polyimide precursor formed from first polyamic acid, second polyamic acid and third polyamic acid. The first polyamic acid can provide rigid molecular chain segments for polyimide precursor, so that polyimide prepared by the subsequent process has good dimensional stability. The long molecular chain segments in the second polyamic acid and the third polyamic acid can effectively reduce the imide group density of the prepared polyimide, reduce the dielectric loss factor and further help to reduce the energy loss of the signal transmission of the subsequent copper foil circuit. In addition, the long molecular chain segment of the third polyamic acid is also helpful to improve the coating property of the polyimide precursor, so as to meet the application requirement.
Detailed Description
The making and using of the embodiments of the present invention are discussed in detail below. However, it is to be understood that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The particular embodiments discussed are merely illustrative and are not meant to limit the scope of the invention.
The polyimide precursor of the present invention is a block polymer composed of a first polyamic acid (A1), a second polyamic acid (A2), and a third polyamic acid (A3). According to the method for producing a polyimide precursor described later, the polyimide precursor produced may have a regular block example structure represented by the following formulas (i-1) to (i-3). It is understood that the polyimide precursor of the present invention is not limited to the following exemplary structures, and other structures of the polyimide precursor can be understood by those skilled in the art according to the manufacturing method described below.
The first polyamic acid (A1), the second polyamic acid (A2) and the third polyamic acid (A3) are all formed by reacting tetracarboxylic dianhydride monomer with diamine monomer. Wherein, based on the structure of the polyamide acid to be prepared, the tetracarboxylic dianhydride monomer and the diamine monomer can be respectively rigid monomer or flexible monomer.
The rigid monomer refers to a monomer structure which is rigid and is not easy to generate rotation change of a molecular structure, so that the rigid monomer is helpful to improve the rigidity of the structure of the formed polymer and improve the dimensional stability of the prepared product. It is understood that the backbone structure of the rigid monomer is generally composed of benzene rings. In other embodiments, the benzene ring of the rigid monomer may also be linked by a ketone group, an amide group, an ester group, and/or other suitable rigid groups.
The term "flexible monomer" as used herein refers to a rigid monomer as described above. Accordingly, the flexible monomer is susceptible to rotational changes in molecular structure and/or has side chain groups that are structurally more flexible. It should be noted that although the flexible monomer is more flexible, the main chain structure may also be composed of benzene rings, wherein the benzene rings of the main chain structure may be linked by ether groups, or the benzene rings of the main chain structure may have alkyl substituents, and have a longer monomer molecular structure. Because the flexible monomer is a monomer with a long molecular structure, the polyimide chain segment prepared later has lower imide functional group density, and can avoid high dielectric loss factor caused by water absorption of imide functional genes, so that the dielectric constant (Dk) and dielectric loss factor (Df) of the material can be effectively reduced. In some examples, when monomers have a longer molecular chain structure, such monomers may be referred to as "pliable monomers" because such monomers may also be effective in reducing the imide functionality density of the resulting polyimide segments. In other words, the "flexible monomer" of the present disclosure primarily helps to reduce the imide functionality density of the polyimide segment formed.
In the method for producing a polyimide precursor of the present invention, the tetracarboxylic dianhydride monomer (A1) and the diamine monomer (b 1) are first subjected to a first reaction to form the polyamic acid (A1). Then, the polyamic acid (A1), the tetracarboxylic dianhydride monomer (a 2), and the diamine monomer (b 2) are subjected to a second reaction to form a block polyamic acid. The block polyamide acid is composed of polyamide acid (A1) and polyamide acid (A2), wherein the polyamide acid (A2) is formed by reacting tetracarboxylic dianhydride monomer (A2) and diamine monomer (b 2).
In order to improve the structural rigidity of the prepared polyimide precursor, rigid monomers can be selected for the diamine monomer (b 1) and the diamine monomer (b 2). In some embodiments, the diamine monomer (b 1) and the diamine monomer (b 2) of the rigid monomer may each include, but are not limited to, p-phenylenediamine (p-PDA), 4' -Diaminobenzanilide (DABA), other suitable diamine monomers, or any mixture of the foregoing.
When the aforementioned first reaction is performed, the tetracarboxylic dianhydride monomer (a 1) may be a rigid monomer. In some embodiments, the rigid monomer tetracarboxylic dianhydride monomer (a 1) may be 3,3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 3', 4' -biphenyl tetracarboxylic dianhydride (s-BPDA), p-phenyl bis (trimellitate) dicarboxylic dianhydride (TAHQ), pyromellitic dianhydride (PMDA), other suitable tetracarboxylic dianhydride monomers, or any mixtures of the foregoing. According to the above description, when the tetracarboxylic dianhydride monomer (A1) and the diamine monomer (b 1) are rigid monomers, the polyamide acid (A1) formed by the reaction can have a more rigid polymer main chain structure, and further has a higher structural rigidity.
In the first reaction, the molar ratio of the tetracarboxylic dianhydride monomer (a 1) to the diamine monomer (b 1) may preferably be 0.9:1 to 1:1. the first reaction is performed using a reaction temperature and other reaction parameters well known to those skilled in the art, and thus, the description thereof is omitted herein. It is understood that the polyamic acid (A1) produced by the first reaction is a colloidal solution. The viscosity of the colloidal solution containing the polyamic acid (A1) may be 20cps to 12000cps, and preferably may be 100cps to 6000cps.
The content of the polyamic acid (A1) may be 20 to 75 mole percent, preferably 20 to 60 mole percent, and more preferably 30 to 50 mole percent, based on 100 mole percent of the content of the polyimide precursor produced.
When the aforementioned second reaction is performed, the tetracarboxylic dianhydride monomer (a 2) may be a monomer having a long chain structure (such as the aforementioned flexible monomer). In some embodiments, the tetracarboxylic dianhydride monomer (a 2) may include, but is not limited to, tetracarboxylic dianhydride monomers having an ether group in the main chain, other suitable tetracarboxylic dianhydride monomers, or any mixture of the above. In some embodiments, the tetracarboxylic dianhydride monomer (a 2) of the monomer having a long chain structure may be p-phenyl bis (trimellitate) di-tetracarboxylic dianhydride (TAHQ), 4' -terephthaloyl diphthalic anhydride (HQDA), other suitable tetracarboxylic dianhydride monomers, or any mixture of the above. Accordingly, in the polyamide acid (A2) formed by the second reaction, the long chain structure of the tetracarboxylic dianhydride monomer (A2) can effectively reduce the dielectric constant and dielectric dissipation factor of the polyamide acid (A2), and the diamine monomer (b 2) of the rigid monomer can still maintain the structural rigidity of the chain segment of the polyamide acid (A2).
In the chemical structure of p-phenyl bis (trimellitate) dicarboxylic dianhydride (TAHQ), although the structure of molecular chain is longer, the benzene rings are connected by ester groups, and the molecules are more difficult to rotate, so that the TAHQ can improve the structural rigidity of the formed material, reduce the imide functional group density of the formed polyimide chain segment, and further reduce the dielectric constant and dielectric loss factor of the material. In other words, p-phenyl bis (trimellitate) di-tetracarboxylic dianhydride (TAHQ) combines the effects of the rigid monomer and the flexible monomer described above.
In the second reaction, the molar ratio of the tetracarboxylic dianhydride monomer (a 2) to the diamine monomer (b 2) is preferably 0.95:1 to 1:1. similarly, the second reaction is performed using a reaction temperature and other reaction parameters well known to those skilled in the art, and thus, the description thereof is omitted herein. The block polyamic acid obtained by the second reaction is a colloidal solution. The viscosity of the colloidal solution is 1000cps to 20000cps, and preferably may be 3000cps to 13000cps.
The content of the polyamic acid (A2) may be 10 to 60 mole percent, preferably 20 to 50 mole percent, and more preferably 25 to 40 mole percent, based on 100 mole percent of the content of the polyimide precursor produced.
In some embodiments, the order of the first and second reactions described above may be interchanged with one another. In other words, the second reaction is performed to form the polyamic acid (A2), and then the first reaction is performed to the polyamic acid (A2), the tetracarboxylic dianhydride monomer (A1), and the diamine monomer (b 1) to obtain the block polyamic acid composed of the polyamic acid (A2) and the polyamic acid (A1).
After the block polyamic acid is prepared, a third reaction is performed on the block polyamic acid, the tetracarboxylic dianhydride monomer (A3) and the diamine monomer (b 3) to obtain the polyimide precursor composed of the block polyamic acid and the third polyamic acid (A3). Wherein the third polyamic acid (A3) is prepared by reacting a tetracarboxylic dianhydride monomer (A3) with a diamine monomer (b 3).
When the third reaction is performed, the diamine monomer (b 3) may be a flexible monomer in order to further reduce the dielectric constant and dielectric dissipation factor of the polyimide precursor. In some embodiments, diamine monomer (b 3) may comprise a diamine monomer having an ether group in the main chain, a diamine monomer having an alkyl group in the side chain, other suitable diamine monomers, or any mixture of the above. In some embodiments, the diamine monomer (b 3) of the pliable monomer may be 1,4-bis (4-aminophenoxy) benzene (TPE-Q), 1, 3-bis (4-aminophenoxy) benzene (TPE-R), other suitable diamine monomers, or any combination of the foregoing. Next, to maintain the segment stiffness of the polyamic acid (A3), the tetracarboxylic dianhydride monomer (A3) may be a rigid monomer. It is understood that the type of the tetracarboxylic dianhydride monomer (a 3) which is the rigid monomer is the same as the tetracarboxylic dianhydride monomer (a 1) described above, and thus the description thereof is omitted herein.
In the third reaction, the molar ratio of the tetracarboxylic dianhydride monomer (a 3) to the diamine monomer (b 3) is preferably 0.98:1 to 1:1. similarly, the third reaction is performed using the reaction temperature and other reaction parameters well known to those skilled in the art, and therefore, the description thereof is omitted herein. The polyimide precursor produced by the third reaction is a colloidal solution (i.e., a polymer solid containing a solvent and the polyimide precursor). The viscosity of the colloidal solution may be 10000cps to 50000cps, and preferably may be 15000 to 40000. In some embodiments, the total solids content of the polyimide precursor may be 10 to 25 weight percent, and preferably may be 14 to 20 weight percent. When the viscosity and the total solid content of the polyimide precursor are in the above ranges, the prepared polyimide precursor can have better film forming property and coating property, and is beneficial to the application requirement of the rear end.
The content of the polyamic acid (A3) may be 10 to 30 mole percent, and preferably 10 to 25 mole percent, based on 100 mole percent of the content of the polyimide precursor produced.
In the prepared polyamide acid (A3), the tetracarboxylic dianhydride monomer (A3) can provide segment rigidity, and the diamine monomer (b 3) can reduce the dielectric constant and dielectric dissipation factor of the polyimide precursor. The polyimide precursor has a larger influence on the flexibility of the polyimide precursor than the tetracarboxylic dianhydride monomer (a 2), but the long molecular structures of the tetracarboxylic dianhydride monomer (a 2) and the diamine monomer (b 3) can effectively reduce the density of the imide functional groups in the prepared polyimide, so that the dielectric constant and the dielectric loss factor can be reduced.
Accordingly, the polyimide film prepared from the polyimide precursor of the present invention can have good dimensional stability and better electrical performance by the flexible chain segments of the polyamic acid (A2) and the polyamic acid (A3) (i.e., the derivative groups of the tetracarboxylic dianhydride monomer (A2) and the diamine monomer (b 3)) in the polyimide precursor, and the rigid chain segments of the polyamic acid (A1) and the polyamic acid (A2) and the polyamic acid (A3) (i.e., the derivative groups of the diamine monomer (b 2) and the tetracarboxylic dianhydride monomer (A3)). Therefore, when the contents of the polyamic acid (A1), the polyamic acid (A2) and the polyamic acid (A3) are respectively in the above-mentioned ranges, the polyimide precursor can have good dimensional stability and good high-frequency transmission performance.
After the third reaction, the obtained polyimide precursor is subjected to a solvent removal step, and then a polymer solid of the polyimide precursor can be obtained. Then, the polyimide precursor in a solid state is further heated to obtain the polyimide. It can be understood that when the polyimide precursor is coated into a film, the solid polyimide precursor obtained by the solvent removal step is a polyamic acid film, and the polyimide film can be obtained after further heating. In some embodiments, the polyimide film may have a thickness of 5 μm to 100 μm.
Accordingly, the polyimide precursor of the present invention can be coated on a copper foil or other substrate, and then the copper foil substrate with a polyimide film can be obtained by using the solvent removal step and the heating step. Then, the copper foil is etched into a required pattern, and the flexible conductive substrate is manufactured.
From the foregoing, it can be seen that the polyimide precursor of the present case is composed of a polyamic acid (A1) having a main rigid segment, a polyamic acid (A2) having a low dielectric loss segment, and a polyamic acid (A3) having a low dielectric loss and a flexible segment. Therefore, the prepared polyimide precursor is a regular block copolymer and has lower charge transfer resistance. In some applications, the dielectric dissipation factor of the polyimide produced may be 0.003 to 0.005 and the dielectric constant may be 3.0 to 3.7. In some examples, the dielectric dissipation factor of the polyimide may be preferably 0.003 to 0.005, and more preferably 0.003 to 0.004. In some examples, the dielectric constant of polyimide may preferably be 3.0 to 3.5.
The following examples are set forth to illustrate the practice of the invention and are not intended to limit the invention thereto, as various modifications and adaptations may be made by those skilled in the art without departing from the spirit and scope of the invention.
Preparation of polyimide film
Example 1
First, 0.015 mol of 4,4' -Diaminobenzanilide (DABA) was added to N-methylpyrrolidone (NMP) to form a diamine monomer solution. Then, 0.015 mol of pyromellitic dianhydride (PMDA) was added to conduct the first stage reaction. After 1 to 4 hours, a colloidal solution (viscosity 40 cps) containing the polyamic acid (A1) was obtained.
Next, 0.075 mol of p-phenylenediamine (p-PDA) and 0.075 mol of p-phenyldi (trimellitate) di-tetracarboxylic dianhydride (TAHQ) are added to the colloidal solution containing the polyamic acid (A1) to perform the second stage reaction. After 1 to 4 hours, a colloidal solution (viscosity 19500 cps) containing the blocked polyamic acid was obtained.
Then, 0.010 mole of 1,4-bis (4-aminophenoxy) benzene (TPE-Q) and 0.010 mole of 3,3', 4' -biphenyltetracarboxylic dianhydride (s-BPDA) were added to the colloidal solution containing the block polyamic acid to perform the third-stage reaction. After 1 to 4 hours, a colloidal solution (viscosity 32900 cps) containing the polyimide precursor was obtained. The content of the polyamic acid (A1) was 15 mol%, the content of the polyamic acid (A2) was 75 mol%, and the content of the polyamic acid (A3) was 10 mol%, based on the content of the prepared polyimide precursor was 100 mol%.
The colloidal solution containing the polyimide precursor is coated into a film, and the film is subjected to a solvent removal step to form a solid polyimide precursor film. Next, the polyimide precursor film was further heated to perform imidization, whereby a polyimide film of example 1 was produced. The obtained polyimide film was evaluated in the following manner of evaluation of dielectric constant and dielectric dissipation factor, and the results are shown in table 1, and are not described in detail herein.
Example 2 and example 3
The polyimide film of example 2 was prepared by using the same procedure as the preparation method of the polyimide film of example 1, except that the tetracarboxylic dianhydride monomer and the diamine monomer were used in different types and amounts in examples 2 to 3. The formulation and evaluation results are shown in Table 1.
Comparative example 1
First, 0.025 mole of 4,4' -Diaminobenzanilide (DABA), 0.015 mole of 1,4-bis (4-aminophenoxy) benzene (TPE-Q), and 0.06 mole of p-phenylenediamine (p-PDA) were added to N-methylpyrrolidone to form a diamine monomer solution. Then, 0.025 mol of 3,3', 4' -diphenyl tetracarboxylic dianhydride (BTDA) and 0.075 mol of 3,3', 4' -diphenyl tetracarboxylic dianhydride (s-BPDA) were added to the diamine monomer solution to perform polymerization. After 1 to 4 hours, a colloidal solution containing a polyimide precursor is obtained.
Next, a colloidal solution containing a polyimide precursor is coated into a film, and subjected to a solvent removal step to form a solid polyimide precursor film. Next, the polyimide precursor film was further heated to perform imidization, whereby a polyimide film of comparative example 1 was produced. The obtained polyimide film was evaluated in the following manner of evaluation of dielectric constant and dielectric dissipation factor, and the results are shown in table 1, and are not described in detail herein.
Comparative example 2
The polyimide film of comparative example 2 was prepared by using the same flow steps as those of the preparation method of the polyimide film of comparative example 1, except that: the diamine monomer used in comparative example 2 was 0.075 mol of p-phenylenediamine (p-PDA) and 0.025 mol of 1,4-bis (4-aminophenoxy) benzene (TPE-Q), and the tetracarboxylic dianhydride monomer was 0.060 mol of 3,3', 4' -biphenyl tetracarboxylic dianhydride (s-BPDA) and 0.040 mol of p-phenyl bis (trimellitate) dicarboxylic dianhydride (TAHQ), and the formulation and evaluation results of the obtained polyimide films are shown in Table 1.
Comparative example 3 and comparative example 4
The polyimide films of comparative examples 3 and 4 were prepared by using the same steps as those of the polyimide film of example 1, except that the tetracarboxylic dianhydride monomer and diamine monomer were used in different types and amounts in comparative examples 3 and 4. The formulation and evaluation results are shown in Table 1.
Dielectric constant and dielectric dissipation factor
First, the polyimide films produced in examples 1 to 3 and comparative examples 1 to 4 were rubbed with alcohol, and then the polyimide films were placed in an oven at 150 ℃. After baking for 30 minutes, it was placed in a room temperature environment (temperature 21 ℃ to 25 ℃ and relative humidity 45% to 55%). After 24 hours, the dielectric constant and dielectric dissipation factor of the polyimide film were measured by a network analyzer (ROHDE & SCHWARZ, inc. and model ZNB-20).
TABLE 1
In table 1, PMDA represents pyromellitic dianhydride (Pyromellitic dianhydride); DABA stands for 4,4'-diaminobenzanilide (4, 4' -diaminobenzanilide); p-PDA represents p-phenylenediamine (1, 4-phenylenediamine); TPE-Q represents 1,4-bis (4-aminophenoxy) benzene (1, 4-bis (4-aminophenoxy) benzene); BTDA stands for 3,3', 4' -benzophenone tetracarboxylic dianhydride (3, 3', 4' -benzophenonetetracarboxylic dianhydride); s-BPDA represents 3,3', 4' -biphenyltetracarboxylic dianhydride (3, 3', 4' -biphenyltetracarboxylic dianhydride); TAHQ represents p-phenyl bis (trimellitate) di-tetracarboxylic dianhydride; HQDA represents 4,4' -terephthaloyl bisphthalic anhydride (1, 4-Bis (3, 4-dicarboxyphenoxy) benzene dianhydride).
From the contents of table 1, the polyimide films prepared in examples 1 to 3 can have low dielectric dissipation factors (Df) and low dielectric constants (Dk) by the method for preparing the polyimide precursor according to the present invention. Among them, when the content of polyamide acid of the long molecular segment (obtained by reacting a rigid diamine monomer with a rigid tetracarboxylic dianhydride monomer) is the largest, the polyimide film produced (i.e., example 2) has lower dielectric dissipation factor and dielectric constant.
In comparative examples 1 and 2, when the polyamic acid precursor is not formed by the staged reaction as described herein, the obtained polyimide film has poor electrical properties. In comparative example 3, although the polyamic acid precursor was prepared in two steps, the polyimide film prepared still had poor electrical properties because the polyimide precursor prepared lacks the polyamic acid (A2) as described in the present application.
Therefore, the preparation method of the polyimide precursor of the invention adopts the steps of reacting for several times and selecting the specific tetracarboxylic dianhydride monomer and diamine monomer to form the block copolymer which is arranged regularly, thereby reducing the dielectric loss and further reducing the energy loss of the subsequent copper foil circuit. Wherein the polyimide precursor is composed of polyamide acid (A1) with a main rigid chain segment, polyamide acid (A2) with a low dielectric loss chain segment and polyamide acid (A3) with a low dielectric loss and a flexible chain segment. Therefore, the polyimide has good dimensional stability and lower dielectric constant and dielectric loss factor, and can reduce the signal loss of signal transmission, thereby meeting the application requirements of high-frequency transmission.
While the present invention has been described with reference to the embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and it is intended that the invention be limited only by the terms of the appended claims.
Claims (5)
1. A method for producing a polyimide precursor, comprising:
performing a first reaction on a first tetracarboxylic dianhydride monomer and a first diamine monomer to form a first polyamic acid;
performing a second reaction on the first polyamic acid, the second tetracarboxylic dianhydride monomer and the second diamine monomer to form a block polyamic acid, wherein the block polyamic acid is composed of the first polyamic acid and the second polyamic acid, and the second polyamic acid is formed by the second tetracarboxylic dianhydride monomer and the second diamine monomer; and
performing a third reaction on the blocked polyamic acid, a third tetracarboxylic dianhydride monomer and a third diamine monomer to form the polyimide precursor, wherein the polyimide precursor is composed of the blocked polyamic acid and the third polyamic acid, the third polyamic acid is formed by the third tetracarboxylic dianhydride monomer and the third diamine monomer, based on the content of the polyimide precursor being 100 mole percent, one of the first polyamic acid or the second polyamic acid is 10 mole percent to 60 mole percent, the other of the first polyamic acid or the second polyamic acid is 20 mole percent to 75 mole percent, and the content of the third polyamic acid is 10 mole percent to 30 mole percent,
wherein one of the first tetracarboxylic dianhydride monomer or the second tetracarboxylic dianhydride monomer is a tetracarboxylic dianhydride monomer having an ether group in the main chain;
the first diamine monomer and the second diamine monomer are not diamine monomers with ether groups on the main chain or diamine monomers with alkyl groups on the side chains, and the third diamine monomer is diamine monomer with ether groups on the main chain or diamine monomer with alkyl groups on the side chains.
2. The method of producing a polyimide precursor according to claim 1, wherein the third tetracarboxylic dianhydride monomer is not a tetracarboxylic dianhydride monomer having an ether group in the main chain.
3. The method of claim 1, wherein the total solids content of the polyimide precursor is 10 to 25 weight percent.
4. A polyimide formed by heating a polyimide precursor prepared by the method of any one of claims 1 to 3, wherein each molecular chain of the polyimide is composed of a first polyamic acid, a second polyamic acid, and a third polyamic acid.
5. The polyimide of claim 4, wherein the polyimide has a dielectric dissipation factor of 0.003 to 0.005 and a dielectric constant of 3.0 to 3.7.
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