CN112979948A - Preparation method of polyimide precursor and polyimide - Google Patents
Preparation method of polyimide precursor and polyimide Download PDFInfo
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- CN112979948A CN112979948A CN202011030363.1A CN202011030363A CN112979948A CN 112979948 A CN112979948 A CN 112979948A CN 202011030363 A CN202011030363 A CN 202011030363A CN 112979948 A CN112979948 A CN 112979948A
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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
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- 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
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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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- C08J2379/00—Characterised by the use of 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; 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 comprises the steps of preparing a polyimide precursor through a first reaction, a second reaction and a third reaction, wherein the polyimide precursor is composed of a first polyamic acid, a second polyamic acid and a third polyamic acid. By using the 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 polyimide precursor, and is especially preparation process of polyimide precursor with low dielectric constant and dielectric loss factor and prepared polyimide.
Background
With the development of the technology industry, high frequency transmission is a main transmission means of wireless communication products, so that a high frequency substrate with a fast transmission rate is the key point of the current development. In order to satisfy the requirement of high frequency transmission, the signal loss of the substrate should be effectively reduced.
Generally, the signal loss in the substrate refers to the insertion loss (insertion loss) of a signal, and the insertion loss is the sum of the reflection loss, the material loss, and the radiation loss. The material loss includes dielectric loss and conductor loss. Dielectric loss is controlled by the insulating layer, and conductor loss is related to the conductivity and surface roughness of the conductive layer. The dielectric loss is calculated by the following formula (I), and it can be known from the formula (I) that lowering the dielectric constant and dielectric dissipation factor of the material can effectively reduce the dielectric loss, thereby facilitating high frequency transmission.
In formula (I), Dk represents the dielectric constant, Df represents the dielectric dissipation factor, and f represents the frequency.
In the existing charge transport substrate, the polyimide copper clad laminate is widely used in electronic products because of its lightness, thinness and flexibility. However, the conventional polyimide film has a high dielectric constant and dielectric dissipation factor, and thus cannot meet the application requirements of high frequency transmission.
In view of the above, it is desirable to provide a method for preparing a polyimide precursor and a polyimide, so as to overcome the defects of the conventional polyimide that the dielectric constant and dielectric dissipation factor are too high.
Disclosure of Invention
Therefore, one aspect of the present invention is to provide a method for preparing a polyimide precursor, wherein a specific tetracarboxylic dianhydride monomer and a diamine monomer are selected to perform a segmented reaction, so as to prepare a block copolymerization monomer in a regular arrangement, thereby reducing the transfer resistance of charges, and thus satisfying 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 above-mentioned method.
According to an aspect of the present invention, a method for preparing a polyimide precursor is provided. The preparation method comprises the step of 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 carried out 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 by a second tetracarboxylic dianhydride monomer and a second diamine monomer. Then, a third reaction is carried out on the block polyamic acid, the third tetracarboxylic dianhydride monomer and the third diamine monomer to form a polyimide precursor. The polyimide precursor is composed of block polyamic acid and third polyamic acid, wherein the third polyamic 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 the side chain.
According to an embodiment of the present invention, the content of the third polyamic acid is 10 mol% to 30 mol% based on the content of the polyimide precursor being 100 mol%.
According to another embodiment of the present invention, the content of the first polyamic acid or the second polyamic acid formed from the first tetracarboxylic dianhydride monomer or the second tetracarboxylic dianhydride monomer is 10 mol% to 60 mol% based on 100 mol% 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 other of the first tetracarboxylic dianhydride monomer or the second tetracarboxylic dianhydride monomer is 20 mol% to 75 mol% based on the content of the polyimide precursor being 100 mol%.
According to another embodiment of the present invention, the first diamine monomer and the second diamine monomer are not a diamine monomer having an ether group in the main chain or a diamine monomer having an alkyl group in the side chain.
According to still another embodiment of the present invention, the third tetracarboxylic dianhydride monomer is not a tetracarboxylic dianhydride monomer having an ether group in its main chain.
According to still another embodiment of the present invention, the total solid content of the polyimide precursor is 10 weight percent 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 above-mentioned preparation method. Each molecular chain of the polyimide is composed of a first polyamic acid, a second polyamic acid and a third polyamic acid.
According to an embodiment of the present 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 the polyimide precursor and the polyimide of the invention utilize the specific tetracarboxylic dianhydride monomer and the diamine monomer to carry out the segmented reaction, thereby forming the block polyimide precursor consisting of the first polyamic acid, the second polyamic acid and the third polyamic acid. The first polyamic acid can provide a rigid molecular chain segment for the polyimide precursor, so that the subsequently prepared polyimide has good size stability. The long molecular chain segments in the second polyamic acid and the third polyamic acid can effectively reduce the density of imide groups of the prepared polyimide, thereby reducing the dielectric loss factor and further being beneficial to reducing the energy loss of subsequent copper foil circuit transmission signals. In addition, the long molecular chain segment of the third polyamic acid is also beneficial to improving the coating property of the polyimide precursor, so that the application requirement can be met.
Detailed Description
The making and using of embodiments of the present invention are discussed in detail below. It should be appreciated, however, that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed are merely illustrative and do not 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 preparing the polyimide precursor described later, the prepared polyimide precursor may have regular block structures represented by the following formulas (i-1) to (i-3). It is to be 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 following manufacturing method.
The first polyamic acid (a1), the second polyamic acid (a2), and the third polyamic acid (A3) are formed by reacting a tetracarboxylic dianhydride monomer with a diamine monomer. The selected tetracarboxylic dianhydride monomer and diamine monomer can be rigid monomer or flexible monomer independently based on the structure of the polyamic acid to be prepared.
The rigid monomer is rigid in monomer structure and not easy to produce rotation change of molecular structure, so that the rigid monomer is favorable to raising the structural rigidity of the formed polymer and improving the size stability of the product. It will be appreciated that the backbone structure of the rigid monomer is generally comprised of benzene rings. In other embodiments, the benzene rings of the rigid monomers may also be linked by ketone groups, amide groups, ester groups, and/or other suitable rigid groups.
The term "flexible monomer" as used herein is used in relation to the rigid monomer. Accordingly, the flexible monomer is susceptible to rotational changes in molecular structure and/or has side chain groups with more flexible structures. 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 connected by ether groups, or the benzene rings of the main chain structure may have alkyl substituents, so as to have a longer monomer molecular structure. Because the flexible monomer is a monomer with a long molecular structure, the polyimide chain segment prepared subsequently has lower imide functional group density, and can avoid high dielectric loss factor caused by water absorption of the imide functional gene, thereby effectively reducing the dielectric constant (Dk) and the dielectric loss factor (Df) of the material. In some instances, monomers can be classified as "flexible monomers" when they have a longer molecular chain structure, since such monomers can also effectively reduce the imide functional group density of the resulting polyimide segment. In other words, the "flexible monomer" in the present case mainly contributes to the reduction of the imide functional group density of the polyimide segment formed.
In the method for preparing the polyimide precursor, the tetracarboxylic dianhydride monomer (a1) and the diamine monomer (b1) are subjected to a first reaction to form the polyamic acid (a 1). Then, the polyamic acid (a1), the tetracarboxylic dianhydride monomer (a2), and the diamine monomer (b2) are subjected to a second reaction to form a block polyamic acid. The block polyamic acid is composed of polyamic acid (A1) and polyamic acid (A2), wherein polyamic acid (A2) is formed by the reaction of 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 used as the diamine monomer (b1) and the diamine monomer (b 2). In some embodiments, the rigid monomeric diamine monomer (b1) and the diamine monomer (b2) may each include, but are not limited to, p-phenylenediamine (p-PDA), 4' -Diaminobenzanilide (DABA), other suitable diamine monomers, or any combination thereof.
When the aforementioned first reaction is carried out, the tetracarboxylic dianhydride monomer (a1) may be a rigid monomer. In some embodiments, the tetracarboxylic dianhydride monomer of a rigid monomer (a1) may be 3,3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 3',4,4' -biphenyl tetracarboxylic dianhydride (s-BPDA), p-phenyl bis (trimellitate) tetracarboxylic dianhydride (TAHQ), pyromellitic dianhydride (PMDA), other suitable tetracarboxylic dianhydride monomers, or any mixture of the above monomers. According to the above description, when the tetracarboxylic dianhydride monomer (a1) and the diamine monomer (b1) are both rigid monomers, the polyamic acid (a1) formed by the reaction can have a stiffer polymer main chain structure, and thus a higher structural rigidity.
In the first reaction, the molar ratio of the tetracarboxylic dianhydride monomer (a1) to the diamine monomer (b1) may preferably be 0.9: 1 to 1: 1. the first reaction is performed by using reaction temperature and other reaction parameters known to those skilled in the art, and therefore, the detailed description thereof is omitted here. It is understood that the polyamic acid (A1) obtained in the first reaction is a colloidal solution. The viscosity of the colloidal solution containing polyamic acid (A1) may be 20cps to 12000cps, and preferably may be 100cps to 6000 cps.
The content of the polyamic acid (a1) may be 20 to 75 mol%, preferably 20 to 60 mol%, and more preferably 30 to 50 mol% based on 100 mol% of the polyimide precursor prepared.
When the aforementioned second reaction is carried out, the tetracarboxylic dianhydride monomer (a2) may be a monomer having a long chain structure (such as the aforementioned flexible monomer). In some embodiments, the tetracarboxylic dianhydride monomer (a2) may include, but is not limited to, tetracarboxylic dianhydride monomers having ether groups in the main chain, other suitable tetracarboxylic dianhydride monomers, or any mixture of the above monomers. In some embodiments, the tetracarboxylic dianhydride monomer (a2) having a long-chain structure monomer may be p-phenyl bis (trimellitate) tetracarboxylic dianhydride (TAHQ), 4' -terephthaloxy diphthalic anhydride (HQDA), other suitable tetracarboxylic dianhydride monomers, or any mixture of the above monomers. Accordingly, in the polyamic 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 polyamic acid (a2), and the diamine monomer (b2) of the rigid monomer can still maintain the structural rigidity of the chain segment of the polyamic acid (a 2).
In the chemical structure of the above-mentioned p-phenyl bis (trimellitate) tetracarboxylic dianhydride (TAHQ), although it has a long molecular chain structure, benzene rings are connected by ester groups, and the molecules are difficult to rotate, so TAHQ can improve the structural rigidity of the formed material, and can also reduce the imide functional group density of the formed polyimide segment, thereby reducing the dielectric constant and dielectric dissipation factor of the material. In other words, p-phenyl bis (trimellitate) tetracarboxylic dianhydride (TAHQ) combines the effects of the rigid monomers and the flexible monomers described above.
In the second reaction, the molar ratio of the tetracarboxylic dianhydride monomer (a2) to the diamine monomer (b2) is preferably 0.95: 1 to 1: 1. similarly, the second reaction is performed by using reaction temperature and other reaction parameters known to those skilled in the art, and therefore, the detailed description thereof is omitted here. The block polyamic acid prepared by the second reaction is a colloidal solution. The viscosity of the colloidal solution is 1000cps to 20000cps, and preferably 3000cps to 13000 cps.
The content of the polyamic acid (a2) may be 10 to 60 mol%, preferably 20 to 50 mol%, and more preferably 25 to 40 mol% based on 100 mol% of the polyimide precursor prepared.
In some embodiments, the order of the first reaction and the second reaction may be interchanged with each other. In other words, the second reaction is performed to form polyamic acid (a2), and then the first reaction is performed on polyamic acid (a2), tetracarboxylic dianhydride monomer (a1), and diamine monomer (b1) to obtain a block polyamic acid composed of polyamic acid (a2) and polyamic acid (a 1).
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 (b3) to obtain the polyimide precursor consisting 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, in order to further reduce the dielectric constant and dielectric dissipation factor of the polyimide precursor, the diamine monomer (b3) may be a flexible monomer. In some embodiments, the diamine monomer (b3) 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 thereof. In some embodiments, the diamine monomer (b3) of the flexible monomer can be 1,4-bis (4-aminophenoxy) benzene (TPE-Q), 1, 3-bis (4-aminophenoxy) benzene (TPE-R), other suitable diamine monomers, or any combination thereof. Next, in order to maintain the segment stiffness of the polyamic acid (a3), the tetracarboxylic dianhydride monomer (a3) may be a stiff monomer. It is understood that the kind of the rigid monomer tetracarboxylic dianhydride monomer (a3) is the same as the above tetracarboxylic dianhydride monomer (a1), and thus will not be described herein again.
In the third reaction, the molar ratio of the tetracarboxylic dianhydride monomer (a3) to the diamine monomer (b3) is preferably 0.98: 1 to 1: 1. similarly, the third reaction is performed by using reaction temperature and other reaction parameters known to those skilled in the art, and therefore, the details thereof are not repeated 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 solid 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 within the above ranges, the prepared polyimide precursor has better film forming property and coating property, thereby being beneficial to the application requirement of the rear end.
The content of the polyamic acid (a3) may be 10 to 30 mol%, and preferably 10 to 25 mol%, based on 100 mol% of the polyimide precursor prepared.
In the prepared polyamic acid (a3), the tetracarboxylic dianhydride monomer (a3) provides segment stiffness, and the diamine monomer (b3) reduces the dielectric constant and dielectric dissipation factor of the polyimide precursor. Since the imide functional group in the polyimide is mainly formed by the tetracarboxylic dianhydride monomer, the diamine monomer (b3) has a greater influence on the flexibility of the polyimide precursor than the tetracarboxylic dianhydride monomer (a2), and the long molecular structures of the tetracarboxylic dianhydride monomer (a2) and the diamine monomer (b3) can effectively reduce the density of the imide functional group in the prepared polyimide, thereby reducing the dielectric constant and the dielectric dissipation factor of the polyimide.
Accordingly, the polyimide film prepared from the polyimide precursor of the present invention has good dimensional stability and good electrical performance due to the flexible segment of the polyamic acid (a2) and the polyamic acid (A3) (i.e., the derivative group of the tetracarboxylic dianhydride monomer (a2) and the diamine monomer (b 3)), and the rigid segment of the polyamic acid (a1), the polyamic acid (a2) and the polyamic acid (A3) (i.e., the derivative group of the diamine monomer (b2) 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 within the ranges described above, the polyimide precursor has good dimensional stability and better high frequency transmission performance.
And after the third reaction, performing a solvent removal step on the obtained polyimide precursor to obtain a polymer solid of the polyimide precursor. Then, the solid polyimide precursor is further heated to obtain polyimide. It can be understood that when the polyimide precursor is coated to form a film, the solid polyimide precursor prepared by the step of removing the solvent is the polyamic acid film, and the polyimide film can be prepared after further heating. In some embodiments, the polyimide film can have a thickness of 5 μm to 100 μm.
Therefore, the polyimide precursor can be coated on copper foil or other base materials, and the copper foil base material with the polyimide film can be prepared by utilizing the solvent removing step and the heating step. Then, the copper foil is etched into a required pattern, and the flexible conductive substrate is manufactured.
According to the above description, the polyimide precursor of the present invention is composed of polyamic acid (a1) having a main rigid segment, polyamic acid (a2) having a low dielectric loss segment, and 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 prepared polyimide may have a dielectric dissipation factor of 0.003 to 0.005 and a dielectric constant of 3.0 to 3.7. In some examples, the dielectric dissipation factor of the polyimide may preferably be 0.003 to 0.005, and more preferably may be 0.003 to 0.004. In some cases, the dielectric constant of the polyimide may preferably be 3.0 to 3.5.
The following examples are provided to illustrate the present invention, but not to limit the invention, and those skilled in the art can make various changes and modifications 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 carry out the first-stage reaction. After 1 to 4 hours, a colloidal solution (viscosity of 40cps) containing polyamic acid (A1) was obtained.
Next, 0.075 mole of p-phenylenediamine (p-PDA) and 0.075 mole of p-phenyl bis (trimellitate) tetracarboxylic dianhydride (TAHQ) were added to the colloidal solution containing polyamic acid (a1) to perform a second-stage reaction. After 1 to 4 hours, a colloidal solution (viscosity 19500cps) containing a block polyamic acid was obtained.
Then, 0.010 mole of 1,4-bis (4-aminophenoxy) benzene (TPE-Q) and 0.010 mole of 3,3',4,4' -biphenyltetracarboxylic dianhydride (s-BPDA) were added to the colloidal solution containing the block polyamic acid to perform a third stage reaction. After 1 to 4 hours, a colloidal solution (viscosity 32900cps) containing the polyimide precursor was obtained. Based on the content of the prepared polyimide precursor being 100 mol%, the content of polyamic acid (a1) being 15 mol%, the content of polyamic acid (a2) being 75 mol%, and the content of polyamic acid (A3) being 10 mol%.
The colloidal solution containing the polyimide precursor is coated to form a film, and the film is subjected to a solvent removal step to form a solid polyimide precursor film. Then, the polyimide precursor film was further heated to perform imidization, whereby the polyimide film of example 1 was obtained. The obtained polyimide film was evaluated in the following manner for evaluating dielectric constant and dielectric dissipation factor, and the results are shown in table 1 and will not be described herein.
Example 2 and example 3
The polyimide film of example 2 was produced by the same procedure as the production 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 moles of 4,4' -Diaminobenzanilide (DABA), 0.015 moles of 1,4-bis (4-aminophenoxy) benzene (TPE-Q), and 0.06 moles of p-phenylenediamine (p-PDA) were added to N-methylpyrrolidone to form a diamine monomer solution. Then, 0.025 mole of 3,3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and 0.075 mole of 3,3',4,4' -biphenyl tetracarboxylic dianhydride (s-BPDA) were added to the diamine monomer solution to carry out polymerization. After 1 to 4 hours, a colloidal solution containing a polyimide precursor is obtained.
Then, a colloidal solution containing a polyimide precursor is coated to form a film, and the film is subjected to a solvent removal step to form a solid polyimide precursor film. Then, the polyimide precursor film was further heated to perform imidization, whereby the polyimide film of comparative example 1 was obtained. The obtained polyimide film was evaluated in the following manner for evaluating dielectric constant and dielectric dissipation factor, and the results are shown in table 1 and will not be described herein.
Comparative example 2
The polyimide film of comparative example 2 used the same flow steps as the method for producing the polyimide film of comparative example 1, except that: comparative example 2 the diamine monomers used were 0.075 mole of p-phenylenediamine (p-PDA) and 0.025 mole of 1,4-bis (4-aminophenoxy) benzene (TPE-Q), and the tetracarboxylic dianhydride monomers were 0.060 mole of 3,3',4,4' -biphenyltetracarboxylic dianhydride (s-BPDA) and 0.040 mole of p-phenylbis (trimellitate) tetracarboxylic dianhydride (TAHQ), and the formulations thereof and the evaluation results of the polyimide films obtained were as shown in table 1.
Comparative examples 3 and 4
The polyimide films of comparative examples 3 and 4 were prepared by the same procedure as the polyimide film of example 1, except that the tetracarboxylic dianhydride monomer and the diamine monomer were used in different amounts and types 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 obtained in examples 1 to 3 and comparative examples 1 to 4 were wiped with alcohol, and then the polyimide films were placed in an oven at 150 ℃. After baking for 30 minutes, the mixture is placed in a room temperature environment (the temperature is 21 ℃ to 25 ℃, and the relative humidity is 45% to 55%). After 24 hours, the dielectric constant and dielectric dissipation factor of the polyimide film were measured by a network analyzer (model ZNB-20, manufactured by ROHDE & SCHWARZ Co.).
TABLE 1
In table 1, PMDA represents Pyromellitic dianhydride (Pyromellitic dianhydride); DABA for 4,4 '-diaminobenzanilide (4, 4' -diaminobenzanilide); p-PDA stands for p-phenylenediamine (1, 4-phenylenediamine); TPE-Q represents 1,4-bis (4-aminophenoxy) benzene (1,4-bis (4-aminophenoxy) bezene); BTDA represents 3,3',4,4' -benzophenone tetracarboxylic dianhydride (3,3',4,4' -benzophenone carboxylic dianhydride); s-BPDA represents 3,3',4,4' -biphenyltetracarboxylic dianhydride (3,3',4,4' -biphenyltetracarboxylic dianhydride); TAHQ represents p-phenyl bis (trimellitate) tetracarboxylic dianhydride; HQDA represents 4,4' -terephthaledioic diphthalic anhydride (1,4-Bis (3,4-dicarboxyphenoxy) benzene dihydride).
As can be seen from table 1, the polyimide films prepared in examples 1 to 3 have lower dielectric loss factor (Df) and dielectric constant (Dk) by the method for preparing the polyimide precursor of the present invention. Wherein, when the content of the polyamic acid of the long molecular chain segment (obtained by reacting the rigid diamine monomer with the rigid tetracarboxylic dianhydride monomer) is the maximum, the polyimide film (i.e., example 2) obtained has a lower dielectric dissipation factor and dielectric constant.
In comparative examples 1 and 2, when the polyamic acid precursor is not formed by the stepwise reaction as described in the present disclosure, the polyimide films obtained have poor electrical performance. In comparative example 3, although the polyamic acid precursor was prepared by two-stage reaction, the polyimide film prepared by the method was poor in electrical performance because the polyimide precursor was poor in the polyamic acid (a 2).
Therefore, the preparation method of the polyimide precursor forms the block copolymer which is regularly arranged by carrying out the fractional reaction and selecting the specific tetracarboxylic dianhydride monomer and the diamine monomer, thereby reducing the dielectric loss and further reducing the energy loss of the subsequent copper foil circuit. The polyimide precursor is composed of polyamic acid (A1) with a main rigid chain segment, polyamic acid (A2) with a low dielectric loss chain segment and polyamic acid (A3) with a low dielectric loss and a flexible chain segment. Therefore, the polyimide formed 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 requirement of high-frequency transmission.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention.
Claims (9)
1. A method for preparing a polyimide precursor, the method comprising:
carrying out a first reaction on a first tetracarboxylic dianhydride monomer and a first diamine monomer to form a first polyamic acid;
carrying out a second reaction on the first polyamic acid, a second tetracarboxylic dianhydride monomer and a second diamine monomer to form a block polyamic acid, wherein the block polyamic acid is composed of the first polyamic acid and a 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 block 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 block polyamic acid and a third polyamic acid, and the third polyamic acid is formed by the third tetracarboxylic dianhydride monomer and the third diamine monomer
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; and is
The third diamine monomer is a diamine monomer with an ether group in the main chain or a diamine monomer with an alkyl group in the side chain.
2. The method of claim 1, wherein the third polyamic acid is present in an amount ranging from 10 mol% to 30 mol% based on 100 mol% of the polyimide precursor.
3. The method of claim 2, wherein the first polyamic acid or the second polyamic acid formed from the first tetracarboxylic dianhydride monomer or the second tetracarboxylic dianhydride monomer is present in an amount of 10 to 60 mol% based on 100 mol% of the polyimide precursor.
4. The method of claim 3, wherein the content of the first polyamic acid or the second polyamic acid formed from the other of the first tetracarboxylic dianhydride monomer or the second tetracarboxylic dianhydride monomer is 20 to 75 mol% based on 100 mol% of the polyimide precursor.
5. The method of claim 1, wherein the first diamine monomer and the second diamine monomer are not a diamine monomer having an ether group in a main chain or a diamine monomer having an alkyl group in a side chain.
6. 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 its main chain.
7. The method of claim 1, wherein the polyimide precursor has a total solid content of 10 wt% to 25 wt%.
8. A polyimide formed by heating a polyimide precursor prepared by the method of any one of claims 1 to 7, wherein each molecular chain of the polyimide is composed of a first polyamic acid, a second polyamic acid, and a third polyamic acid.
9. The polyimide of claim 8, 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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| CN116217929A (en) * | 2022-12-07 | 2023-06-06 | 杭州福斯特电子材料有限公司 | Polyimide resin, film and preparation method thereof, flexible copper-clad plate and electronic device |
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