TW201712058A - Polyamic acid blend and method for preparing the same and method for preparing polyimide film - Google Patents

Abstract

A method for preparing polyamic acid blend is provided. First, a first polyamic acid solution and a second polyamic acid solution are prepared, wherein the first polyamic acid solution includes a polyamic acid having a repeating unit represented by formula 1, and the second polyamic acid solution includes a polyamic acid having a repeating unit represented by formula 2, formula 1 formula 2, Wherein A is; B is; Ar isor, and X is single bond, -O-, -SO2-, C(CF3)2 or -CO- and Ar' is or, and X' is single bond, -O-, -SO2-, C(CF3)2 or -CO-.

Description

Polylysine mixture and preparation method thereof, and preparation method of polyimine film

The invention relates to a preparation method of a polyaminic acid mixture and a preparation method of the polyimine membrane, and in particular to a preparation method of a polyaminic acid mixture using a specific diamine monomer and a polyimine A method of preparing a film.

Polyimine is widely used in various fields as a forming material, a composite material, and an electric/electronic material because of its excellent heat resistance, mechanical properties, and electrical properties. The properties of the polyimine can be regulated by the monomers used. Based on this, in order to effectively control the characteristics without increasing the complexity of the reaction, the polyimine is usually synthesized by copolymerization using two or more kinds of diamine monomers and/or two or more dianhydride monomers. . However, such a synthesis method must fully consider the reactivity of various diamine monomers and dianhydride monomers, and the factors such as the feeding time, which may affect the reaction, and thus tend to cause an increase in production cost and a decrease in productivity.

The invention provides a preparation method of a polyaminic acid mixture, which can obtain a uniformly mixed polyaminic acid mixture, thereby obtaining a dielectric constant, a dielectric loss, a thermal expansion coefficient, a glass transition temperature, and an elastic modulus. Polyimine membranes whose properties are effectively regulated.

The preparation method of the polyaminic acid mixture of the present invention comprises the following steps. First, a first polyaminic acid solution and a second polyaminic acid solution are prepared, wherein the first polyamic acid solution comprises a polylysine having a repeating unit represented by Formula 1, and a second poly-proline The solution includes polylysine having a repeating unit represented by Formula 2, Formula 1 Equation 2, where A is , B is , Ar is or And X is a single bond, -O-, -SO ₂ -, C(CF ₃ ) ₂ or -CO-, and Ar' is or And X' is a single bond, -O-, -SO ₂ -, C(CF ₃ ) ₂ or -CO-. Next, the first polyaminic acid solution is mixed with the second polyaminic acid solution.

In one embodiment of the present invention, in the polyamic acid mixture described above, polylysine having a repeating unit represented by Formula 1 and polylysine having a repeating unit represented by Formula 2 The content of the polyaminic acid having a repeating unit represented by Formula 1 is more than 0 wt% to 90 wt%, based on the total weight.

In an embodiment of the invention, the Ar is And X is a single bond, and Ar' is And X' is a single bond or -O-.

In an embodiment of the present invention, the method for preparing the polyamic acid mixture described above further comprises the following steps. Preparing a third polyaminic acid solution; and mixing the first polyamic acid solution, the second polyaminic acid solution, and the third polyaminic acid solution.

In an embodiment of the invention, the third polyaminic acid solution comprises polylysine having a repeating unit represented by Formula 3: Equation 3, where D is , Ar'' is or And X'' includes a single bond, -O-, -SO ₂ -, C(CF ₃ ) ₂ or -CO-.

In an embodiment of the invention, the Ar'' is And X'' includes a single bond.

In one embodiment of the present invention, in the polyamic acid mixture described above, polylysine having a repeating unit represented by Formula 1, polylysine having a repeating unit represented by Formula 2 And the polyglycine having a repeating unit represented by Formula 3 is contained in an amount of more than 0% by weight to 20% by weight based on the total weight of the polyamic acid having a repeating unit represented by Formula 3.

In one embodiment of the present invention, the solvent of the first polyaminic acid solution and the solvent of the second polyaminic acid solution respectively include N-methyl-2-pyrrolidone (NMP), N, N-dimethyl N, N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), hexamethylphosphoramide or meglumine Phenol (m-cresol).

The preparation method of the polyimine membrane of the present invention comprises the following steps. First, a polyaminic acid mixture is prepared by the above-described preparation method of a polyamic acid mixture. Next, after applying the polyaminic acid mixture to the substrate, heat treatment is performed.

The polyaminic acid mixture of the present invention comprises a first polyamic acid solution and a second polyamic acid solution, wherein the first polyamic acid solution comprises a polylysine having a repeating unit represented by Formula 1, and The second polyaminic acid solution includes polylysine having a repeating unit represented by Formula 2, Formula 1 Equation 2, where A is , B is , Ar is or And X is a single bond, -O-, -SO ₂ -, C(CF ₃ ) ₂ or -CO-, and Ar' is or And X' is a single bond, -O-, -SO ₂ -, C(CF ₃ ) ₂ or -CO-.

In an embodiment of the invention, the Ar is And X is a single bond, and Ar' is And X' is a single bond or -O-.

In an embodiment of the present invention, the polyamic acid mixture further includes a third polyaminic acid solution comprising polylysine having a repeating unit represented by Formula 3: Equation 3, where D is , Ar'' is or And X'' includes a single bond, -O-, -SO ₂ -, C(CF ₃ ) ₂ or -CO-.

In an embodiment of the invention, the Ar'' is And X'' includes a single bond.

Based on the above, the preparation method of the polyaminic acid mixture proposed by the present invention is the first poly-proline solution having the poly-proline which has the repeating unit represented by Formula 1 and having the formula 2 The repeating unit of the poly-proline acid second polyaminic acid solution is mixed to obtain a polyaminic acid mixture in a uniformly mixed state. Further, by using the polyaminic acid mixture of the present invention, a polyimide film having an effective property such as a dielectric constant, a dielectric loss, a thermal expansion coefficient, a glass transition temperature, and an elastic modulus can be obtained.

The above described features and advantages of the present invention will be more apparent from the following description.

In the present specification, the range represented by "a value to another value" is a schematic representation that avoids enumerating all the values in the range in the specification. Therefore, the recitation of a particular range of values is intended to include any value in the range of values and the range of values defined by any value in the range of values, as in the specification. The scope is the same.

Herein, the structure of a polymer or a group is sometimes represented by a skeleton formula. This representation can omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. Of course, if the atom or atomic group is clearly drawn in the structural formula, the person who prescribes it shall prevail.

An embodiment of the present invention provides a method for preparing a polyaminic acid mixture, comprising the steps of: Step A: preparing a first polyamic acid solution and a second polyaminic acid solution; Step B: using the first polyamine The acid solution is mixed with the second polyaminic acid solution.

Step A will be described first.

The first polyaminic acid solution includes polylysine having a repeating unit represented by Formula 1, and the second polyaminic acid solution includes polylysine having a repeating unit represented by Formula 2: Formula 1 Equation 2.

In the above formula 1, A is , Ar is or And X is a single bond, -O-, -SO ₂ -, C(CF ₃ ) ₂ or -CO-, and in the above formula 2, B is , Ar' is or And X' is a single bond, -O-, -SO ₂ -, C(CF ₃ ) ₂ or -CO-.

Specifically, Ar and Ar' are each a residue other than two carboxylic anhydride groups (-(CO) ₂ O) in the tetracarboxylic dianhydride compound; and A and B are respectively two amino groups in the diamine compound. Residues other than (-NH ₂ ). That is, in the present embodiment, polylysine having a repeating unit represented by Formula 1 and polylysine having a repeating unit represented by Formula 2 are all permeated with a tetracarboxylic dianhydride compound and A diamine compound is obtained by reaction. Herein, the tetracarboxylic dianhydride compound used to prepare the polyamic acid is referred to as a dianhydride monomer, and the diamine compound is referred to as a diamine monomer.

Specifically, the diamine monomer used to prepare the polyamic acid having the repeating unit represented by Formula 1 is cyclohexanediamine (CHDA), and the dianhydride monomer is 3,3'. 4,4'-Biphenyltetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic anhydride (Bis-(3-phthalyl anhydride) Ether, ODPA, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (3,3',4,4'-Benzophenonetetracarboxylic dianhydride, BTDA), 3,3',4, 4'-Diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroisopropene) diacetic anhydride (4,4'- (Hexafluoroisopropylidene)diphthalic Anhydride (6FDA) or pyromellitic dianhydride (1,2,4,5-Benzenetetracarboxylic anhydride, PMDA for short); and polyamine for preparing a repeating unit represented by Formula 2. The diamine monomer is 4,4'-diaminodicyclohexyl methane (MBCHA), and the dianhydride monomer is also BPDA, ODPA, BTDA, DSDA, 6FDA or PMDA. Further, in one embodiment, the dianhydride monomer used to prepare the polyamic acid having the repeating unit represented by Formula 1 is BPDA, and is used to prepare a polyamine having a repeating unit represented by Formula 2. The acid dianhydride monomer is BPDA or ODPA.

It is worth mentioning that the polylysine having the repeating unit represented by Formula 1 is CHDA as a diamine monomer, whereby the polyimine prepared therefrom has a low coefficient of thermal expansion and high thermal stability. And a high elastic modulus; and the polyaminic acid having the repeating unit represented by Formula 2 is MBCHA as a diamine monomer, whereby the polyimine prepared therefrom has a low dielectric constant and a low Dielectric loss.

Further, in the present embodiment, the molecular weight of the polylysine having the repeating unit represented by Formula 1 is at least 8,000 or more, and the molecular weight of the polyamine having the repeating unit represented by Formula 2 is at least 8,000 or more.

Further, polylysine having a repeating unit represented by Formula 1 and polylysine having a repeating unit represented by Formula 2 are reacted in a solvent by a diamine monomer and a dianhydride monomer. Got it. That is, in the present embodiment, the first polyaminic acid solution and the second polyamic acid solution respectively include a polylysine having a repeating unit represented by Formula 1 and having a formula represented by Formula 2 In addition to the polyamine of the repeating unit, a solvent is also included.

In detail, the preparation method of the first polyaminic acid solution includes, for example, first, after dissolving CHDA as a diamine monomer in a solvent at a temperature of room temperature (25 ^o C to 35 ^o C), BPDA, ODPA, BTDA, DSDA, 6FDA, or PMDA of the dianhydride monomer is added for mixing. Subsequently, at a temperature of 70 ^o C to 110 ^o C after the reaction period, the temperature was lowered to room temperature the reaction was continued for another period of time. In the foregoing steps, the solvent is, for example, N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), dimethyl Dimethyl sulfoxide (DMSO), dimethylformamide (DMF), hexamethylphosphoramide or m-cresol; reaction time is, for example, 12 hours to 24 hours And the solid content of the first polyaminic acid solution is, for example, 10% to 20%.

In addition, the preparation method of the second polyaminic acid solution includes, for example, first, after dissolving MBCHA as a diamine monomer in a solvent in a water bath (room temperature), BPDA, ODPA, BTDA as a dianhydride monomer. , DSDA, 6FDA or PMDA is added for mixing. Next, stirring was continued in a water bath (room temperature) to carry out the reaction. In the foregoing step, the solvent is, for example, NMP, DMAc, DMSO, DMF, hexamethylphosphonamide or m-cresol; the reaction time is, for example, 16 hours to 48 hours; and the solid content of the first polyaminic acid solution is, for example, 10% to 20%.

Next, step B will be described below.

In the present embodiment, the mixing ratio of the first polyamic acid solution to the second polyamic acid solution is not particularly limited. In detail, the first polyamic acid solution and the second polyamic acid solution may be mixed in a specific ratio according to actual needs. That is, it is within the scope of the present invention to prepare a polyamido acid mixture by mixing a first polyamic acid solution with a second polyaminic acid solution.

Further, as described above, since the polyimine prepared by the polyamic acid having the repeating unit represented by Formula 1 has a low thermal expansion coefficient, high thermal stability, and high elastic modulus, The polyimine prepared by the polyamine of the repeating unit represented by Formula 2 has a low dielectric constant and a low dielectric loss, so that the thermal expansion coefficient and thermal stability of the polyimide can be used according to practical applications. The mixing modulus, the dielectric constant, and the dielectric loss are adjusted to adjust the mixing ratio of the first polyamic acid solution to the second polyaminic acid solution.

Further, in one embodiment, in the polyamido acid mixture, the total weight of the polyaminic acid having the repeating unit represented by Formula 1 and the polylysine having the repeating unit represented by Formula 2 The polyamine acid having a repeating unit represented by Formula 1 is contained in an amount of more than 0% by weight to less than 90% by weight. By the content of the polyaminic acid having the repeating unit represented by Formula 1 in the polyamido acid mixture being within the above range, the polyimine obtained by the first polyaminic acid solution and Polyimine with lower dielectric loss compared to polyimine prepared from a second polyaminic acid solution.

In still another embodiment, in the polyamido acid mixture, the polyamic acid having the repeating unit represented by Formula 1 and the poly-proline having the repeating unit represented by Formula 2 The content of the polyamic acid having the repeating unit represented by Formula 1 is more than 0 wt% to 30 wt%, based on the total weight. By the content of the polyaminic acid having the repeating unit represented by Formula 1 in the polyamido acid mixture being within the above range, the polyimine obtained by the first polyaminic acid solution and A polyimine having a lower dielectric loss and a lower dielectric constant than a polybenzamine prepared by a second polyaminic acid solution alone.

It is worth mentioning that, as described above, although having a repeating unit represented by formula 1 of polyamide acid undergoes reaction process at a temperature of 70 ^o C to 110 ^o C, and having the formula 2 The poly-proline of the repeating unit is only reacted at room temperature, but since the poly-proline mixture is obtained by mixing the first polyamic acid solution and the second poly-proline solution, The amine acid mixture can exhibit not only a uniform mixed state, but also a polylysine having a repeating unit represented by Formula 1 and a polyamic acid having a repeating unit represented by Formula 2 can have a desired molecular weight.

In addition, in the present embodiment, the preparation method of the polyaminic acid mixture may optionally include the steps of: preparing a third polyaminic acid solution; and the first polyamic acid solution and the second polyamic acid solution and The third polyaminic acid solution is mixed.

The third polyaminic acid solution includes, for example, polylysine having a repeating unit represented by Formula 3: Equation 3, where D is , Ar'' is or And X'' includes a single bond, -O-, -SO ₂ -, C(CF ₃ ) ₂ or -CO-.

Similarly, as described above, Ar'' is a residue other than two carboxylic anhydride groups (-(CO) ₂ O) in the tetracarboxylic dianhydride compound; and D is a diamine compound other than two amino groups ( Residues other than -NH ₂ ). Specifically, the diamine monomer used to prepare the polylysine having the repeating unit represented by Formula 3 is 4,4'-diaminobenzanilide (abbreviated as DABA). The dianhydride monomer is BPDA, ODPA, BTDA, DSDA, 6FDA or PMDA. Further, in one embodiment, the dianhydride monomer used to prepare the polyamic acid having the repeating unit represented by Formula 3 is BPDA.

Similarly, as described above, the polyglycolic acid having a repeating unit represented by Formula 3 is obtained by reacting a diamine monomer and a dianhydride monomer in a solvent. That is, the third polyaminic acid solution includes a solvent in addition to the polylysine having a repeating unit represented by Formula 3.

In detail, the preparation method of the third polyaminic acid solution includes, for example, first, after dissolving DABA as a diamine monomer in a solvent in a water bath (room temperature), BPDA, ODPA as a dianhydride monomer , BTDA, DSDA, 6FDA or PMDA are added for mixing. Next, stirring was continued in a water bath (room temperature) to carry out the reaction. In the foregoing step, the solvent is, for example, NMP, DMAc, DMSO, DMF, hexamethylphosphonamide or m-cresol; the reaction time is, for example, 12 hours to 36 hours; and the solid content of the third polyamidic acid solution is, for example, 5% to 15%.

In the present embodiment, the mixing ratio of the first polyamic acid solution, the second polyamic acid solution, and the third polyamic acid solution is not particularly limited. That is, the first polyamic acid solution, the second polyamic acid solution, and the third polyamic acid solution may be mixed in a specific ratio according to actual needs.

In one embodiment, in the polyaminic acid mixture, polylysine having a repeating unit represented by Formula 1, polyamic acid having a repeating unit represented by Formula 2, and having Formula 3 The polyglycine having a repeating unit represented by Formula 3 is preferably contained in an amount of more than 0 wt% to 20 wt%, more preferably more than 0 wt%, based on the total weight of the polyamine of the repeating unit. 10 wt%.

Another embodiment of the present invention provides a method for preparing a polyimide film, comprising the steps of: preparing a polyamido acid mixture by a method for preparing a polyamido acid mixture in any of the foregoing embodiments, and then The polyamic acid mixture is applied to a substrate and then subjected to heat treatment.

Specifically, in the present embodiment, examples of the coating method include a blade coating method, a roll coating method, a spin coating method, and a printing method.

In the present embodiment, examples of the substrate include a glass substrate, a plastic substrate, a ceramic substrate, and a metal substrate. Examples of the material of the glass substrate include soda glass, potassium glass, borosilicate glass, quartz glass, aluminosilicate glass, lead glass, and the like. Examples of the material of the plastic substrate include a thermosetting resin (for example, an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, etc.), and a thermoplastic resin (for example, a phenoxy resin, a polyether oxime, a polyfluorene, and a poly Polyphenylene sulfone, etc.). Examples of the material of the ceramic base material include alumina, aluminum nitride, zirconium oxide, ruthenium, tantalum nitride, tantalum carbide, and the like. Examples of the material of the metal substrate include aluminum, zinc, copper, and the like. Further, the substrate may have a structure in which two or more layers of the above-mentioned plastic substrate, glass substrate, ceramic substrate, and metal substrate are laminated.

In the present embodiment, the main purpose of performing the heat treatment after coating is to remove the solvent in the polyamido acid mixture and to cause the polyglycine to undergo a dehydration ring closure reaction. The heat treatment method is, for example, heat baking, and the method of heat baking is, for example, a method of performing heat treatment in an oven or an infrared furnace, a method of performing heat treatment on a hot plate, or the like. In one embodiment, the heat treatment comprises, for example, baking the coated polyaminic acid mixture at 140 ^o C to 160 ^o C for 5 minutes to 10 minutes to remove the solvent, and then heating to 300 ^o. Bake at C to 350 ^o C for 20 minutes to 30 minutes.

In addition, the polyimide film has a thickness of between about 14 μm and 22 μm.

It is to be noted that, as described above, since the polyimine prepared by the polyamic acid having the repeating unit represented by Formula 1 has a low thermal expansion coefficient, high thermal stability, and high elastic modulus, The polyimine prepared by the polyamine of the repeating unit represented by Formula 2 has a low dielectric constant and a low dielectric loss, so that the first polyaminic acid solution and the second poly-proline are mixed. The properties of the dielectric constant, dielectric loss, thermal expansion coefficient, glass transition temperature, and elastic modulus of the polyimide film obtained by the solution of the polyaminic acid mixture can be effectively regulated.

Further, as described above, since the polyaminic acid mixture is obtained by mixing the first polyamic acid solution and the second polyaminic acid solution, it is not necessary to consider the reaction of the diamine monomer and the dianhydride monomer. The mixture can be directly mixed by factors such as the nature and the feeding time point, and the polyaminic acid having the repeating unit represented by Formula 1 and the polyamine having the repeating unit represented by Formula 2 can be obtained. The acid has a polyamic acid mixture of the desired molecular weight. As a result, the method for preparing the polyimide film can have low production cost and high productivity.

Features of the present invention will be more specifically described below with reference to Examples 1-17 and Comparative Examples 1-3. Although the following examples are described, the materials used, the amounts and ratios thereof, the processing details, the processing flow, and the like can be appropriately changed without departing from the scope of the invention. Therefore, the invention should not be construed restrictively by the examples described below.

The information on the main materials and equipment used in the preparation of the polyimide films of Examples 1-17 and Comparative Examples 1-3 is as follows.

3,3',4,4'-biphenyltetracarboxylic dianhydride (abbreviated as BPDA): purchased from JFE Chemical Co., Ltd.

Cyclohexanediamine (CHDA for short): purchased from Aldrich.

4,4'-Diaminodicyclohexylmethane (abbreviated as MBCHA): purchased from TCI Corporation.

4,4'-oxydiphthalic anhydride (ODPA): purchased from JFE Chemical Co., Ltd.

4,4'-Diaminobenzoquinone (abbreviated as DABA): purchased from TCI Corporation.

N-methyl-2-pyrrolidone (abbreviated as NMP) was purchased from Boeing.

Low force meter: manufactured by Mitutoyo America Corporation under the name Litematic LV-50A. < Example 1> Preparation of Polyproline Mixture

Preparation of the first polyaminic acid solution: 0.2938 mol (86.45 g) of BPDA was added after dissolving 0.2938 mol (33.55 g) of CHDA in a water bath (room temperature) in 680 g of NMP as a solvent. Next, at 110 ^o C, after the reaction was 0.5 hours, and then be cooled to room temperature for 12 hours, i.e., the first polyamide acid solution obtained CHDA / BPDA obtained, a solid content of 15%.

Preparation of a second polyaminic acid solution: 0.2378 mol (69.97 g) of BPDA was added after dissolving 0.2378 mol (50.03 g) of MBCHA in a water bath (room temperature) in 680 g of NMP as a solvent. Next, a second polyaminic acid solution prepared by MBCHA/BPDA was obtained in a water bath (room temperature) for 24 hours, and the solid content was 15%.

After completing the preparation of the first polyamic acid solution and the second polyaminic acid solution, using the polylysine in the first polyaminic acid solution and the polyamine in the second polyaminic acid solution The total weight of the acid, the content of the poly-proline in the first polyaminic acid solution is 10 wt% and the content of the poly-proline in the second polyamic acid solution is 90 wt%, which will be A polyamic acid solution and a second polyamic acid solution were mixed to obtain the polyamido acid mixture of Example 1. Further, in the following, the content ratio between poly-proline is defined as the mixing ratio between the poly-proline solutions. Preparation of polyimine film

The coating method using a doctor blade polyamide acid mixture of Example 1 50 ml of the heat-resistant coating on a glass substrate, and then baked at 140 ^o C 10 min to remove the NMP. Followed, the heat-resistant glass substrate is placed in a dehydration ring-closure reaction for 30 minutes of 350 ^o C anaerobic conditions, to obtain a configuration example of a heat resistant polyimide film on a glass substrate of FIG. Finally, the heat-resistant glass substrate was removed by water to obtain the polyimide film of Example 1, in which the thickness was measured with a low force meter to obtain a thickness of about 14 μm to 22 μm. Example 2-6

The polyaminic acid mixture and the polyimide film of Example 2-6 were produced according to the same manufacturing procedure as in Example 1, and the difference mainly lies in the first polyaminic acid solution and the second polyaminic acid solution. The mixing ratio is as shown in Table 1, for example. Further, in Examples 2 to 6, the thickness of the polyimide film was also shown in Table 1. Example 7

The polyamido acid mixture and the polyimide film of Example 7 were produced according to the same manufacturing procedure as in Example 1, except that the polyglycine mixture of Example 7 was prepared by mixing CHDA/BPDA. The first poly-proline solution, the second poly-proline solution prepared by MBCHA/BPDA, and the third poly-proline solution prepared by DABA/BPDA. Wherein, the step of preparing the third polyaminic acid solution prepared by DABA/BPDA is as follows: after dissolving 0.23 mol (52.30 g) of DABA in a water bath (room temperature), 680 g of NMP as a solvent, 0.23 Mole (67.70 g) of BPDA was added. Next, a reaction of the reaction was carried out for 24 hours in a water bath (room temperature) to obtain a third polyaminic acid solution prepared by DABA/BPDA, and the solid content was 15%.

Further, in Example 7, the mixing ratio of the first polyaminic acid solution, the second polyaminic acid solution to the third polyaminic acid solution, and the thickness of the polyimide film were shown in Table 1, respectively. Example 8

The polyaminic acid mixture and the polyimide film of Example 8 were produced according to the same manufacturing procedure as in Example 7, and the difference mainly lies in the first polyaminic acid solution, the second polyaminic acid solution, and the first The mixing ratio of the trimeric acid solution is as shown in Table 1, for example. Further, in Example 8, the thickness of the polyimide film is shown in Table 1. Example 9

The polyamido acid mixture and the polyimide film of Example 9 were produced according to the same manufacturing procedure as in Example 1, except that the polyglycine mixture of Example 9 was prepared by mixing CHDA/BPDA. The first polyaminic acid solution and the second polyamic acid solution prepared by MBCHA/ODPA are obtained. Wherein, the step of preparing the second polyaminic acid solution prepared by MBCHA/ODPA is as follows: after dissolving 0.307 mol (64.66 g) of MBCHA in a water bath (room temperature), 640 g of NMP as a solvent, 0.307 The ODPA of mol (95.34 g) was added. Next, in a water bath (room temperature), after 24 hours of reaction, a second polyaminic acid solution obtained by MBCHA/ODPA was obtained, and the solid content was 20%.

Further, in Example 9, the mixing ratio of the first polyaminic acid solution and the second polyaminic acid solution, and the thickness of the polyimide film are shown in Table 1, respectively. Example 10-14

The polyaminic acid mixture and the polyimide film of Examples 10-14 were produced according to the same manufacturing procedure as in Example 9, and the difference was mainly in that the first polyaminic acid solution and the second polyaminic acid solution were The mixing ratio is as shown in Table 1, for example. Further, in Examples 10 to 14, the thickness of the polyimide film was shown in Table 1. Example 15

The polyamido acid mixture and the polyimide film of Example 15 were produced according to the same manufacturing procedure as in Examples 7-8, mainly differing in that the polyamido acid mixture of Example 15 was permeated with CHDA/BPDA. The obtained first polyamic acid solution, the second polyamic acid solution prepared by MBCHA/ODPA, and the third polyaminic acid solution prepared by DABA/BPDA are obtained. Further, in Example 15, the mixing ratio of the first polyamic acid solution, the second polyamic acid solution and the third polyaminic acid solution, and the thickness of the polyimide film are shown in Table 1, respectively. Example 16-17

The polyaminic acid mixture and the polyimide film of Examples 16-17 were produced according to the same manufacturing procedure as in Example 15, and the difference was mainly in that the first polyaminic acid solution and the second polyaminic acid solution were used. And the mixing ratio of the third polyaminic acid solution, the detailed ratio of which is shown in Table 1, for example. Further, in Examples 16 to 17, the thickness of the polyimide film was shown in Table 1. Comparative example 1

Coating method using a doctor blade coating a second polyamide acid solution 50 ml of MBCHA / BPDA obtained on a heat-resistant glass substrate, and then baked at 140 ^o C 10 min to remove the NMP. Followed, the heat-resistant glass substrate is placed in a dehydration ring-closure reaction for 30 minutes of 350 ^o C anaerobic conditions, to obtain the configuration of Comparative Example 1 polyimide film on a heat-resistant glass substrate. Finally, the heat-resistant glass substrate was removed by water to obtain a polyimide film of Comparative Example 1, in which the thickness was measured with a low force meter to obtain a thickness of about 14 μm to 22 μm.

That is, the difference between Comparative Example 1 and Example 1-17 was mainly that in Comparative Example 1, a polyaminic acid solution was simply used to prepare a polyimide film. Comparative example 2

The polyimide film of Comparative Example 2 was produced according to the same manufacturing procedure as in Comparative Example 1, and the difference was mainly in that Comparative Example 2 was prepared by using a first polyaminic acid solution prepared by using CHDA/BPDA. Amine film. Further, in Comparative Example 2, the thickness of the polyimide film is shown in Table 1. Comparative example 3

The polyimide film of Comparative Example 3 was produced according to the same manufacturing procedure as in Comparative Example 1, and the difference was mainly in that Comparative Example 3 was prepared by using a second polyaminic acid solution prepared by MBCHA/ODPA. Amine film. Further, in Comparative Example 3, the thickness of the polyimide film was shown in Table 1. Table 1 Continued Table 1

Thereafter, the polyimine films of Examples 1-17 and Comparative Examples 1-3 were subjected to dielectric constant, dielectric loss, coefficient of thermal expansion (CTE), glass transition temperature, thermal cracking temperature, and elasticity, respectively. Determination of the modulus. The description of the above measurement is as follows, and the results of the measurement are shown in Table 2. <Measurement of dielectric constant and dielectric loss>

First, the polyimide films of Examples 1-17 and Comparative Examples 1-3 were each formed into a film having a width of 7 cm × 10 cm. Subsequently, the membrane is placed after those baked in an oven at a temperature of 130 ^o C for 2 hours, it was placed in seven days under atmospheric conditions. Thereafter, the dielectric constant and dielectric loss of the films were measured using a dielectric constant measuring device (manufactured by ROHDE & SCHWARZ under the name R&S®ZVB20V Vector Network Analyzer), wherein The measurement frequency is 10 GHz. In the industry-set standard, the dielectric constant of the polyimide film is 3.2 or less, and the lower the value, the better the dielectric property; and the dielectric loss is 0.01 or less, and the lower the value, the better the dielectric property. <Measurement of Thermal Expansion Coefficient>

First, the polyimide films of Examples 1-17 and Comparative Examples 1-3 were each formed into a film having a width of 2 mm × 30 mm. Next, using a thermomechanical analyzer (manufactured by Seiko Instrument Inc., the device name is EXSTAR 6000), the membranes were set under a nitrogen atmosphere and a temperature increase rate of 10 ^o C/min. The temperature is raised from 30 ^o C to 450 ^o C, and the average of the dimensional changes between 50 ^o C and 200 ^o C is obtained to obtain the coefficient of thermal expansion. In the industry-set standard, the thermal expansion coefficient of the polyimide film is as close as possible to the copper foil, and the copper foil is 17 ppm/ ^o C or less. <Measurement of glass transition temperature>

First, the polyimide films of Examples 1-17 and Comparative Examples 1-3 were each formed into a film having a width of 5 mm × 40 mm. Next, using a dynamic mechanical analyzer (manufactured by Seiko Instrument Inc., the device name is EXSTAR 6100), the membranes were set under a nitrogen atmosphere and a temperature increase rate of 10 ^o C/min. The temperature measured from 30 ^o C to 450 ^o C and the loss tangent (tan δ) change rate is measured as the glass transition temperature. <Measurement of Thermal Cracking Temperature>

First, 0.5 to 0.8 g of the polyimide films of Examples 1 to 17 and Comparative Examples 1 to 3 were weighed and used as test films, respectively. Next, using a thermogravimetric loss analyzer (manufactured by Seiko Instrument Inc., equipment name: EXSTAR 6000), the film was set under a nitrogen atmosphere and a temperature increase rate of 10 ^o C/min. The temperature was raised from 30 ^o C to 600 ^o C, and the temperature measured when the film lost 5% by weight was taken as the thermal cracking temperature. In the industry-set standards, the thermal cracking temperature of the polyimide film generally needs to be at least 400 ^o C or more, and the larger the value, the better the thermal stability of the insulating film. <Measurement of elastic modulus>

First, the polyimine films of Examples 1-17 and Comparative Examples 1-3 were respectively made into a dumbbell (dog puncture) having a width (punctuation pitch) of 25.4 mm × 3.2 mm, and the thickness thereof was measured. Next, using a universal testing machine (manufactured by Shimadzu Scientific Instruments Co., Ltd. (SHIMADZU), the device name is AG-1S), the test samples were stretched to the stretching length under the condition that the tensile strength was initially set to zero. Break and determine the tear strength at this time. Young's Modulus can be regarded as an index of the degree of elastic deformation of a material. The larger the value, the greater the stress required for elastic deformation, that is, the greater the stiffness of the material; The smaller the numerical value, the better the flexibility or flexibility. Table 2

As can be seen from Table 2, the polyimine films of Examples 1 to 6 and Examples 9 to 14 have dielectric constant, dielectric loss, thermal expansion coefficient, glass transition temperature, thermal cracking temperature, and elastic modulus. Have a good performance. This shows that a polyaminic acid mixture prepared by mixing a first polyamic acid solution and a second polyaminic acid solution to prepare a polyimide film can effectively regulate the dielectric constant of the polyimide film. Electrical losses, thermal expansion coefficients, glass transition temperatures, and elastic modulus to meet actual demand.

Further, as is clear from Table 2, the polyimide films of Examples 1 to 3 all have lower dielectric loss than the polyimide films of Comparative Example 1 and Comparative Example 2; and Comparative Examples 2 The polyimide films of Examples 9 to 13 all had lower dielectric loss than the polyimide film of Comparative Example 3. This shows that in the case of preparing a polyimide film mixture by mixing a first polyaminic acid solution and a second polyaminic acid solution in a specific ratio to obtain a polyimide film, it is possible to obtain a single polyfluorene. The polyimine film prepared by the amine acid solution has a lower dielectric loss than the polyimide film prepared by the second polyamic acid solution alone.

Further, as is clear from Table 2, the polyimide films of Examples 1 to 2 have lower dielectric loss and dielectric constant than the polyimide films of Comparative Example 1 and Comparative Example 2; As compared with the polyimide membranes of Comparative Example 2 and Comparative Example 3, the polyimide films of Examples 9 to 10 all had lower dielectric loss and dielectric constant. This shows that in the case of preparing a polyimide film mixture by mixing a first polyaminic acid solution and a second polyaminic acid solution in a specific ratio to obtain a polyimide film, it is possible to obtain a single polyfluorene. The polyimine film prepared by the amine acid solution has lower dielectric loss and dielectric constant than the polyimide film prepared by the second polyamic acid solution.

Further, from the measurement results of Examples 7 to 8 and Examples 15 to 17, it is understood that the thermal expansion coefficient and the modulus of elasticity of the polyimide film can be effectively controlled by mixing the third polyaminic acid solution. .

The present invention has been disclosed in the above embodiments, but it is not intended to limit the invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

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Claims (13)

A method for preparing a polyamido acid mixture, comprising: preparing a first polyamic acid solution and a second polyamic acid solution, wherein the first polyamic acid solution comprises a repeating unit having the formula 1 Polylysine, and the second polyamic acid solution comprises polylysine having a repeating unit represented by Formula 2, Formula 1 Equation 2, where A is , B is , Ar is or And X is a single bond, -O-, -SO ₂ -, C(CF ₃ ) ₂ or -CO-, and Ar' is or And X' is a single bond, -O-, -SO ₂ -, C(CF ₃ ) ₂ or -CO-; and the first polyamic acid solution and the second polyamic acid solution are subjected to mixing. The method for producing a polyaminic acid mixture according to claim 1, wherein in the polyaminic acid mixture, the poly-proline having the repeating unit represented by Formula 1 and the The polyamino acid having a repeating unit represented by Formula 1 is contained in an amount of more than 0% by weight to less than 90% by weight based on the total weight of the polyamic acid having a repeating unit represented by Formula 2. A method for preparing a polyamido acid mixture as described in claim 1, wherein Ar is And X is a single bond, and Ar' is And X' is a single bond or -O-. The method for preparing a polyaminic acid mixture according to claim 1, further comprising: preparing a third polyaminic acid solution; and the first polyamic acid solution and the second polyamine The acid solution is mixed with the third polyaminic acid solution. The method for producing a polyaminic acid mixture according to claim 4, wherein the third polyaminic acid solution comprises polylysine having a repeating unit represented by Formula 3: Equation 3, where D is , Ar'' is or And X'' includes a single bond, -O-, -SO ₂ -, C(CF ₃ ) ₂ or -CO-. A method for preparing a polyamido acid mixture as described in claim 4, wherein Ar'' is And X'' includes a single bond. The method for producing a polyaminic acid mixture according to claim 4, wherein in the polyamido acid mixture, the polylysine having the repeating unit represented by Formula 1, the The polyfluorene having the repeating unit represented by Formula 2 and the polyfluorene having the repeating unit represented by Formula 3, the polyfluorene having a repeating unit represented by Formula 3 The content of the amine acid is more than 0 wt% to 20 wt%. The method for preparing a polyaminic acid mixture according to claim 1, wherein the solvent of the first polyaminic acid solution and the solvent of the second polyamic acid solution respectively comprise N-methyl- 2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), dimethylformamide (DMF) , hexamethylphosphoramide or m-cresol. A method for preparing a polyimine film, comprising: preparing a polyamido acid mixture by a method for preparing a polyaminic acid mixture according to any one of claims 1 to 8; The proline mixture is applied to the substrate; and heat treated. A polyaminic acid mixture comprising: a first polyaminic acid solution, wherein the first polyamic acid solution comprises a polylysine having a repeating unit represented by Formula 1, and a second polyfluorene An amine acid solution, the second polyaminic acid solution comprising polylysine having a repeating unit represented by Formula 2, Formula 1 Equation 2, where A is , B is , Ar is or And X is a single bond, -O-, -SO ₂ -, C(CF ₃ ) ₂ or -CO-, and Ar' is or And X' is a single bond, -O-, -SO ₂ -, C(CF ₃ ) ₂ or -CO-. Polyurethane mixture as described in claim 10, wherein Ar is And X is a single bond, and Ar' is And X' is a single bond or -O-. The polyaminic acid mixture according to claim 10, further comprising a third polyaminic acid solution comprising a polyfluorene having a repeating unit represented by Formula 3. Amino acid: Equation 3, where D is , Ar'' is or And X'' includes a single bond, -O-, -SO ₂ -, C(CF ₃ ) ₂ or -CO-. A method for preparing a polyamido acid mixture according to claim 12, wherein Ar'' is And X'' includes a single bond.