TWI522393B - Polymer, insulating film, and flexible copper clad laminate - Google Patents

Description

Polymer, insulating film and soft copper foil substrate

The present invention relates to a polymer, an insulating film, and a flexible copper foil substrate, and more particularly to a polymer having a low dielectric constant and a low dielectric loss, an insulating film including the polymer, and the like Soft copper foil substrate.

As electronic products gradually move toward thin and light trends, the demand for flexible circuit boards has also increased significantly. The main upstream material of the flexible circuit board is a flexible copper foil substrate, which is usually produced by coating or bonding a polyimide pigment polymer onto a copper foil. The polyiminoimine polymers currently used in the industry have good heat resistance and dimensional stability, but the dielectric properties are not good, which limits their application range. Therefore, how to reduce the dielectric constant of the polyimine polymer to have good dielectric properties, thermal stability and dimensional stability is currently an extremely desirable target in this field.

The present invention provides a polymer comprising a novel quinone imine repeating unit and an insulating film comprising the polymer having a low dielectric constant and a low dielectric loss, and the insulating film is suitable for use in a soft copper foil substrate .

The polymer of the present invention comprises at least 25 mol% of the repeating unit represented by Formula 1: Wherein Ar is a tetravalent organic group derived from a tetracarboxylic dianhydride containing an aromatic group, and A is a divalent organic group derived from a diamine containing a cyclohexane group, and the carbon number of the divalent organic group is 8 To 18.

In an embodiment of the invention, the number of repeating units represented by the above formula 1 is between 10 and 2,000.

In an embodiment of the invention, the Ar includes and At least one of, and B includes a single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -SO ₂ - or -CO-.

In an embodiment of the invention, the above A includes , , , and At least one of them.

The polymer of the present invention includes the structure represented by Formula 2: Wherein Ar is a tetravalent organic group derived from a tetracarboxylic dianhydride containing an aromatic group, A is a divalent organic group derived from a diamine containing a cyclohexane group, and the carbon number of the divalent organic group is 8 to 18, Ψ for other repeat units and 0.25 X 1.

In an embodiment of the invention, the Ar includes and At least one of, and B includes a single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -SO ₂ - or -CO-.

In an embodiment of the invention, the above A includes , , , and At least one of them.

In an embodiment of the invention, the above Ψ is expressed by Equation 3: Wherein Φ is a divalent organic group derived from a diamine containing an aromatic group or a cyclic aliphatic group, and Ar includes and At least one of, and B includes a single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -SO ₂ - or -CO-.

In an embodiment of the invention, the above Φ includes and At least one of them.

In an embodiment of the invention, the above Φ includes and And versus The molar ratio is 9:1 to 1:9.

The insulating film of the present invention includes the aforementioned polymer.

In an embodiment of the invention, the insulating film has a dielectric constant of 2.8 to 3.5 and a dielectric loss of 0.005 to 0.014.

The flexible copper foil substrate of the present invention comprises a copper foil and the aforementioned insulating film. The insulating film is disposed on the copper foil.

In one embodiment of the invention, the soft copper foil substrate further includes an adhesive layer disposed between the copper foil and the insulating film.

Based on the above, the polymer proposed by the present invention is manufactured by using a diamine monomer having a specific structure and a specific ratio and a dianhydride monomer containing an aromatic group, so that the polymer and the insulating film including the same can simultaneously have a low medium. Electrical constant, low dielectric loss and high thermal stability.

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.

One embodiment of the present invention provides a polymer comprising at least 25 mol% of a repeating unit represented by Formula 1:

In the above formula 1, Ar is a tetravalent organic group derived from a tetracarboxylic dianhydride containing an aromatic group. That is, Ar is a residue other than the two carboxylic anhydride groups (-(CO) ₂ O) in the tetracarboxylic dianhydride containing an aromatic group. Herein, the aromatic group-containing tetracarboxylic dianhydride is also referred to as a dianhydride monomer. Further, in the present embodiment, in the case of preparing a repeating unit represented by Formula 1, a dianhydride monomer or a plurality of dianhydride monomers may be employed.

Specifically, Ar includes and At least one of, and B includes a single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -SO ₂ - or -CO-. That is, the aromatic group-containing tetracarboxylic dianhydride is, for example, pyromellitic dianhydride (1,2,4,5-Benzenetetracarboxylic anhydride, PMDA for short), 3,3', 4,4'- Bismuth tetracarboxylic dianhydride (3,3',4,4'-Biphenyltetracarboxylic dianhydride, BPDA for short), 4,4'-oxyphthalic anhydride (Bis-(3-phthalyl anhydride) ether, ODPA for short) , 3,3',4,4'-Benzophenonetetracarboxylic dianhydride (BTDA).

When the repeating unit represented by Formula 1 contains a tetravalent organic group derived from a tetracarboxylic dianhydride containing an aromatic group, it is possible to impart high thermal stability to the polymer. In addition, since the above-mentioned aromatic group-containing tetracarboxylic dianhydride is inexpensive, the use of the aromatic group-containing tetracarboxylic dianhydride can not only have a property satisfying market demand, but also a manufacturing cost thereof. It can also be reduced to make it industrially valuable.

In the above formula 1, A is a divalent organic group derived from a diamine containing a cyclohexane group, and the divalent organic group has a carbon number of 8 to 18, preferably 8 to 16. That is, A is a residue other than two amino groups (-NH ₂ ) in the diamine containing a cyclohexane group. Herein, the cyclohexane group-containing diamine is also referred to as a diamine monomer. Further, in the present embodiment, in the case of preparing a repeating unit represented by Formula 1, a diamine monomer or a plurality of diamine monomers may be employed.

Specifically, A includes , , , and At least one of them. That is, the cyclohexane group-containing diamine is, for example, 4,4'-diaminodicyclohexyl methane (abbreviated as MBCHA) or 1,3-bis(aminomethyl). Cyclohexane (1,3-Di(aminomethyl)cyclohexane), 1,4-di(aminomethyl)cyclohexane, bis(aminomethyl)cyclohexane [2.2. 1] bis(aminomethyl)bicyclo[2.2.1]heptane), 4,4'-Methylenebis(2-methylcyclohexylamine).

It is worth mentioning that due to 4,4'-diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis (ammonia) Methyl)bicyclo[2.2.1]heptane or diaminomethylcyclohexylmethane has low dielectric constant, low dielectric loss and good thermal stability, and the polymer permeation includes derivatives derived from 4,4'-di Aminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(aminomethyl)bicyclo[2.2.1]heptane and two The repeating unit represented by Formula 1 of the divalent organic group of at least one of aminomethylcyclohexylmethane can be obtained not only to have high thermal stability but also to adjust its dielectric constant and dielectric loss. In detail, the structure does not contain a derivative derived from 4,4'-diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane. Compared with the divalent organic group polymer of bis(aminomethyl)bicyclo[2.2.1]heptane and diaminomethylcyclohexylmethane, the structure contains derivatized from 4,4'-diaminodicyclohexylmethane. , 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(aminomethyl)bicyclo[2.2.1]heptane and diaminomethylcyclohexyl The divalent organic based polymer of at least one of methane has a lower dielectric constant and dielectric loss.

Further, as described above, the repeating unit represented by Formula 1 is a quinone imine repeating unit obtained by carrying out a ruthenium reaction of a dianhydride monomer and a diamine monomer. In detail, the oxime imidization reaction is carried out in a solvent such as N-methyl-2-pyrrolidone (NMP) or N,N-dimethylacetamide (N, N-dimethylacetamide). , DMAc), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), hexamethylphosphoniumamine (hexamethylphosphoramide) or m-cresol. Further, the oxime imidization ratio of the oxime imidization reaction was 100%.

Further, in the present embodiment, the number of repeating units represented by Formula 1 is between 10 and 2,000, preferably between 20 and 1,500.

Another embodiment of the present invention provides a polymer comprising the structure represented by Formula 2:

In the above formula 2, the definition of Ar is the same as the definition of Ar in the formula 1, and the definition of A is the same as the definition of A in the formula 1. From another point of view, the structure represented by Formula 2 contains the repeating unit represented by Formula 1.

In the above formula 2, hydrazine is another repeating unit. That is, Ψ is a repeating unit different from the repeating unit represented by Formula 1. In detail, Ψ may be a repeating unit represented by Formula 3:

In the above formula 3, the definition of Ar is the same as the definition of Ar in the formula 1.

In the above formula 3, Φ is a divalent organic group derived from a diamine containing an aromatic group or a cyclic aliphatic group. That is, Φ is a divalent organic group derived from a diamine which does not contain a cyclohexane group. Further, in the present embodiment, when preparing other repeating units represented by Formula 3, a diamine monomer or a plurality of diamine monomers may be employed.

Specifically, Φ includes and At least one of them. That is, the diamine containing an aromatic group or a cyclic aliphatic group is, for example, p-Phenylenediamine (PDA), 4,4'-diaminophenylphenylaniline (4, 4). '-Diaminobenzanilide, referred to as DABA).

It is to be noted that the other repeating unit represented by Formula 3 has an intermolecular force enhanced by the passage of a divalent organic group derived from p-phenylenediamine and/or 4,4'-diaminophenylphenylaniline. In detail, p-phenylenediamine has a π-electron system and has good symmetry. By containing a divalent organic group derived from p-phenylenediamine, the intermolecular π-π stacking force can be Reinforced to form a π-π stacking structure; and 4,4'-diaminophenylphenylaniline has a guanamine group belonging to a hydrogen bonding group, such that other repeating units represented by Formula 3 When a divalent organic group derived from 4,4'-diaminophenylphenylaniline is contained, a hydrogen bond can be formed between molecules.

In the above formula 2, 0.25 X 1, preferably 0.5 X 1. That is to say, the structure shown in Formula 2 may contain only the repeating unit represented by Formula 1 without containing other repeating units, or contain other repeating units in a specific ratio. From another point of view, in the present embodiment, when preparing the structure represented by Formula 2, a diamine monomer or a plurality of diamine monomers may be employed.

Further, when X=1, the structure represented by Formula 2 contains only the repeating unit represented by Formula 1 and does not contain other repeating units. When the polymer includes only the structure represented by Formula 2, it is a diamine containing a cyclohexane group (ie, 4,4'-diaminodicyclohexylmethane, 1,3-bis(aminomethyl)). Cyclohexane, 1,4-bis(aminomethyl)cyclohexane, double A polyilylimine polymer prepared as a diamine monomer by at least one of (aminomethyl)bicyclo[2.2.1]heptane and diaminomethylcyclohexylmethane.

It is worth noting that, as mentioned above, 4,4'-diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, Bis(aminomethyl)bicyclo[2.2.1]heptane or diaminomethylcyclohexylmethane has low dielectric constant, low dielectric loss and good thermal stability, and aromatic acid-containing tetracarboxylic acid The anhydride has high heat-stable properties, so that the polymer including the structure represented by Formula 2 at this time has not only high thermal stability but also low dielectric constant and dielectric loss.

Further, as described above, the polyimine polymer is prepared in the presence of a solvent such as NMP, DMAc, DMSO, DMF, hexamethylphosphonium or m-cresol, and the The polyamidene polymer has a ruthenium iodide ratio of 100%.

And when 0.25 When X < 1, the structure shown in Formula 2 contains other repeating units greater than 0 and less than or equal to 75 mole percent. Further, when the polymer includes only the structure represented by Formula 2 and the other repeating unit is represented by Formula 3, the polymer is other than the cyclohexane containing the cyclohexane group. A polyimine polymer prepared from a diamine monomer.

Specifically, in one embodiment, the structure shown in Formula 2 can be prepared by using 4,4'-diaminodicyclohexylmethane and p-phenylenediamine as the diamine monomer; in another embodiment, The structure shown in Formula 2 can also be prepared by using 4,4'-diaminodicyclohexylmethane and 4,4'-diaminophenylhydrazine aniline as the diamine monomer; or in still another embodiment, The structure shown in Formula 2 can also be used by using 4,4'-diaminobicyclohexane. Methane, p-phenylenediamine and 4,4'-diaminophenylphenylaniline are prepared as diamine monomers. In addition, when 4,4'-diaminodicyclohexylmethane, p-phenylenediamine and 4,4'-diaminophenylphenylaniline are simultaneously used as the diamine monomer, p-phenylenediamine and 4,4' The molar ratio of the diaminobenzoylaniline is, for example, from 9:1 to 1:9, preferably from 4:1 to 3:2. However, the present invention is not limited thereto, and it is understood by those having ordinary knowledge in the art that as long as a diamine containing a cyclohexane group and an aromatic group or a cyclic aliphatic group but not containing a cyclohexane group are used at the same time. The preparation of the structure represented by Formula 2 as a diamine monomer falls within the scope of the present invention.

It is worth noting that, as described above, the inclusion of a divalent organic group derived from p-phenylenediamine in the structure enhances the intermolecular π-π stacking force and contains derived from 4,4'-diaminobenzene. The divalent organic group of mercaptoaniline may have a hydrogen bond between the molecules, and therefore, the polymer including the structure represented by Formula 2 has a derivatization derived from p-phenylenediamine and/or 4,4'-diaminophenyl fluorenyl group. The divalent organic group of aniline can reduce its thermal expansion coefficient. In detail, the inclusion of the formula 2 includes a derivative derived from p-phenylenediamine as compared with a polymer not containing a divalent organic group derived from p-phenylenediamine and 4,4'-diaminophenylphenylaniline. And/or a polymer having a divalent organic group structure of 4,4'-diaminophenyl phenylaniline has a lower coefficient of thermal expansion.

That is, the polymer including the structure represented by Formula 2 is derived from 4,4'-diaminodicyclohexylmethane, 1,3, which has good thermal stability and can lower the dielectric constant and dielectric loss. - at least two of bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(aminomethyl)bicyclo[2.2.1]heptane and diaminomethylcyclohexylmethane In addition to the divalent organic group of one, further integration can enhance the intermolecular force The divalent organic group of phenylenediamine and/or 4,4'-diaminophenylphenylaniline makes it possible to achieve a good balance between physical properties such as dielectric properties, thermal stability and dimensional stability. That is, the polymer including the structure shown in Formula 2 has both a low dielectric constant, a low dielectric loss, a thermal expansion coefficient similar to that of the copper foil, and a high thermal stability property.

Further, the polymer of the present invention may be in the form of a film, a powder, a solution or the like. Hereinafter, the form of the polymer as a film will be described as an example.

Another embodiment of the present invention provides an insulating film comprising the aforementioned polymer. In detail, the insulating film has a dielectric constant of 2.8 to 3.5 and a dielectric loss of 0.005 to 0.014.

It should be noted that, as described above, since the polymer can have not only a low dielectric constant, a low dielectric loss, and a high thermal stability, but also has a thermal expansion coefficient similar to that of the copper foil, the insulating film can also have a low value. The dielectric constant, the low dielectric loss and the high thermal stability, and further have a thermal expansion coefficient similar to that of the copper foil, whereby the insulating film is suitable for use in a soft copper foil substrate not only in compliance with industrial requirements, but also has industrial value.

Another embodiment of the present invention further provides a flexible copper clad laminate (FCCL) comprising a copper foil and the foregoing insulating film, wherein the insulating film serves as a flexible substrate in the flexible copper foil substrate. As the copper foil, any of the copper foils used in the soft copper foil substrate known to those skilled in the art can be used, and for example, it can be an electrolytic copper foil or a rolled copper foil, and the thickness is not particularly limited.

Further, the flexible copper foil substrate of the present invention further includes an adhesive layer disposed between the copper foil and the insulating film for allowing the copper foil to closely adhere to the insulating film. The material of the adhesive layer is, for example, a thermosetting resin.

It should be noted that, as described above, since the insulating film has a low dielectric constant, low dielectric loss, and high thermal stability, the soft copper foil substrate can have good reliability and process yield. In detail, the insulating film has a low dielectric constant and a low dielectric loss, thereby reducing electrical interference between lines in a flexible circuit board made of a soft copper foil substrate, and helping to avoid parasitic capacitance and its derivatives. The power load, and avoiding signal delay or interference, resulting in increased power consumption. In addition, since the insulating film can further have a coefficient of thermal expansion similar to that of the copper foil, the dimensional change caused by the high-temperature process of the insulating film due to the manufacture of the flexible copper foil substrate can be effectively suppressed, thereby preventing the occurrence of alignment shift and improving the soft copper. The dimensional stability of the foil substrate.

Features of the present invention will be more specifically described below with reference to Examples 1-12 and Comparative Example 1. Although the following examples 1-12 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.

Information on the main materials and equipment used in the preparation of the insulating films of Examples 1 to 7 and Comparative Example 1 is as follows.

4,4'-Diaminodicyclohexylmethane: purchased from TCI Corporation.

P-phenylenediamine: purchased from Eastcom Chemical Company.

4,4'-Diaminophenylhydrazinoaniline: purchased from TCI Corporation.

3,3',4,4'-biphenyltetracarboxylic dianhydride: purchased from JFE Chemical Co., Ltd.

Pyromellitic dianhydride: purchased from JFE Corporation.

4,4'-oxydiphthalic anhydride: purchased from JFE Corporation.

N-methyl-2-pyrrolidone: purchased from TEDIA Corporation.

Low force meter: manufactured by Mitutoyo America Corporation under the name Litematic LV-50A.

Example 1

0.1486 mol (31.27 g) of 4,4'-diaminodicyclohexylmethane (hereinafter abbreviated as MBCHA) was dissolved in a water bath (room temperature) in 420 g of N-methyl-2-pyrrolidone as a solvent (hereinafter referred to as NMP). 0.1486 mol (43.73 g) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter referred to as BPDA) was added under a water bath. Next, a polyamine solution having a solid content of 15% was obtained after 5 to 7 hours of reaction in a water bath. Thereafter, the polyamic acid solution was baked at 150 ° C for 10 minutes, and then subjected to hydrazine imidization (dehydration cyclization) for 30 to 40 minutes under a nitrogen atmosphere of 350 ° C to obtain the insulation of Example 1. The film, wherein the ruthenium imidation ratio was 100%, and the thickness was measured with a low force meter to obtain a thickness of about 12 μm to 22 μm.

Example 2

In a water bath (room temperature), 0.0438 mol (9.21 g) of MBCHA was weighed and dissolved in 425 g of NMP as a solvent. 0.1753 mol (51.57 g) of BPDA was added under a water bath. Next, 0.1315 mol (14.21 g) of p-phenylenediamine (hereinafter referred to as PDA) was added to the aforementioned solution. Thereafter, after 5 to 7 hours of the reaction, a polyamine solution having a solid content of 15% was obtained. Next, the polyamic acid solution was baked at 150 ° C for 10 minutes, and then subjected to a hydrazine imidization reaction under a nitrogen atmosphere of 350 ° C for 30 to 40 minutes to obtain an insulating film of Example 2, wherein The amination ratio was 100%, and the thickness was measured with a low force meter to obtain a thickness of about 12 μm to 22 μm.

Example 3

The insulating film of Example 3 was fabricated in accordance with the same manufacturing procedure as in Example 2, except that in Example 2, the molar ratio of MBCHA, PDA and BPDA was 0.25:0.75:1, and in the example In 3, the molar ratio of MBCHA, PDA and BPDA is 0.5:0.5:1. Further, in Example 3, the solid content of the polyaminic acid solution, the oxime imidization ratio, and the thickness of the insulating film are shown in Table 1, respectively.

Example 4

The insulating film of Example 4 was fabricated in accordance with the same manufacturing procedure as in Example 2, except that in Example 2, the molar ratio of MBCHA, PDA, and BPDA was 0.25:0.75:1, and in the examples. In 4, the molar ratio of MBCHA, PDA and BPDA is 0.75: 0.25:1. Further, in Example 4, the solid content of the polyaminic acid solution, the ruthenium iodide ratio, and the thickness of the insulating film are shown in Table 1, respectively.

Example 5

In a water bath (room temperature), 0.074 mol (15.56 g) of MBCHA and 0.074 mol (16.81 g) of 4,4'-diaminophenylphenylaniline (hereinafter referred to as DABA) were weighed and dissolved in 425 g of NMP as a solvent. in. 0.148 mol (42.64 g) of BPDA was added under a water bath. Thereafter, a polyamine solution having a solid content of 15% was obtained after 5 to 7 hours of reaction in a water bath. Next, the polyamic acid solution was baked at 150 ° C for 10 minutes, and then subjected to a hydrazine imidization reaction under a nitrogen atmosphere of 350 ° C for 30 to 40 minutes to obtain an insulating film of Example 5, wherein The amination ratio was 100%, and the thickness was measured with a low force meter to obtain a thickness of about 12 μm to 22 μm.

Example 6

The insulating film of Example 6 was fabricated in accordance with the same manufacturing procedure as in Example 5, except that in Example 5, the molar ratio of MBCHA, DABA and BPDA was 0.5:0.5:1, and in the examples In 6, the molar ratio of MBCHA, DABA and BPDA was 0.75: 0.25:1. Further, in Example 6, the solid content of the polyaminic acid solution, the oxime imidization ratio, and the thickness of the insulating film are shown in Table 1, respectively.

Example 7

0.0806 mol (16.95 g) of MBCHA, 0.0644 mol (6.97 g) of PDA and 0.0161 mol (3.66 g) of DABA were dissolved in a water bath (room temperature). 425 g of NMP as a solvent. 0.1611 mol (47.42 g) of BPDA was added under a water bath. Thereafter, a polyamine solution having a solid content of 15% was obtained after 5 to 7 hours of reaction in a water bath. Next, the polyamic acid solution was baked at 150 ° C for 10 minutes, and then subjected to hydrazine imidization reaction under a nitrogen atmosphere of 350 ° C for 30 to 40 minutes to obtain an insulating film of Example 7, wherein The amination ratio was 100%, and the thickness was measured with a low force meter to obtain a thickness of about 12 μm to 22 μm.

Example 8

The insulating film of Example 8 was fabricated in accordance with the same manufacturing procedure as in Example 7, except that in Example 7, the molar ratio of MBCHA, PDA, DABA, and BPDA was 0.5:0.4:0.1:1. In Example 8, the molar ratio of MBCHA, PDA, DABA, and BPDA was 0.5:0.35:0.15:1. Further, in Example 8, the solid content of the polyaminic acid solution, the oxime imidization ratio, and the thickness of the insulating film are shown in Table 1, respectively.

Example 9

The insulating film of Example 9 was fabricated in accordance with the same manufacturing procedure as in Example 7, except that in Example 7, the molar ratio of MBCHA, PDA, DABA, and BPDA was 0.5:0.4:0.1:1. In Example 9, the molar ratio of MBCHA, PDA, DABA, and BPDA was 0.5:0.3:0.2:1. Further, in Example 9, the solid content of the polyaminic acid solution, the oxime imidization ratio, and the thickness of the insulating film are shown in Table 1, respectively.

Example 10

In a water bath (room temperature), 0.2334 mol (50.90 g) of pyromellitic dianhydride (hereinafter abbreviated as PMDA) was weighed and dissolved in 200 g of NMP as a solvent, and 0.2334 mol (49.10 g) of MBCHA was weighed and dissolved. In 200 g of NMP as a solvent. Next, the PMDA solution was uniformly mixed with the MBCHA solution, and then, after 10 to 12 hours of reaction in a water bath, a polyamine solution having a solid content of 20% was obtained. Next, the polyamic acid solution was baked at 150 ° C for 10 minutes, and then subjected to a hydrazine imidization reaction under a nitrogen atmosphere of 350 ° C for 30 to 40 minutes to obtain an insulating film of Example 10, wherein The amination ratio was 100%, and the thickness was measured with a low force meter to obtain a thickness of about 12 μm to 22 μm.

Example 11

The insulating film of Example 11 was produced in the same manufacturing procedure as in Example 10 except that in Example 10, the dianhydride monomer used was PMDA, and in Example 11, the used film was used. The dianhydride monomer is 4,4'-oxydiphthalic anhydride (hereinafter referred to as OPDA). Further, in Example 11, the solid content of the polyaminic acid solution, the oxime imidization ratio, and the thickness of the insulating film are shown in Table 1, respectively.

Example 12

In a water bath (room temperature), 0.1723 mol (36.25 g) of MBCHA and 0.0191 mol (4.35 g) of DABA were weighed and dissolved in 400 g of NMP as a solvent. Under a water bath, 0.1914 mol (59.40 g) of OPDA was added. After that, in the water bath Next, after 5 to 7 hours of reaction, a polyamine solution having a solid content of 20% was obtained. Next, after the polyamic acid solution was baked at 150 ° C for 10 minutes, the hydrazide reaction was carried out in a nitrogen atmosphere at 350 ° C for 30 to 40 minutes to obtain an insulating film of Example 12, wherein The amination ratio was 100%, and the thickness was measured with a low force meter to obtain a thickness of about 12 μm to 22 μm.

Comparative example 1

The insulating film of Comparative Example 1 was produced in the same manufacturing procedure as in Example 1, except that in Example 1, the diamine monomer used was MBCHA, and in Comparative Example 1, the used The diamine monomer is DABA. Further, in Comparative Example 1, the solid content of the polyaminic acid solution, the ruthenium imidization ratio, and the thickness of the insulating film are shown in Table 1, respectively.

Thereafter, the insulating films of Examples 1 to 10 and Comparative Example 1 were each measured for dielectric constant, dielectric loss, coefficient of thermal expansion (CTE), glass transition temperature, and thermal cracking temperature. 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 insulating films of Examples 1 to 10 and Comparative Example 1 were each formed into a film having a width of 7 cm × 10 cm. Next, the films were baked in an oven at a temperature of 130 ° C for 2 hours, and then placed in an atmosphere for five days. 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, in the application of the flexible copper foil substrate, the dielectric constant of the insulating film is 3.2 or less to meet the product requirements, and the lower the value, the better the dielectric property; and the dielectric loss of the insulating film is 0.01 or less to meet the product requirements. And the lower the value, the better the dielectric properties.

<Measurement of Thermal Expansion Coefficient>

First, the insulating films of Examples 1 to 10 and Comparative Example 1 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 nitrogen gas atmosphere and the temperature increase rate were set to 10 ° C / min. The film was heated from 30 ° C to 450 ° C under the conditions, and an average value of the dimensional change amount between 50 ° C and 200 ° C was determined to obtain a thermal expansion coefficient. In the industry, in the application of a flexible copper foil substrate, a thermal expansion coefficient of 30 ppm/° C. or less is considered to be similar to a thermal expansion coefficient (17 ppm/° C.) of the copper foil.

<Measurement of glass transition temperature>

First, the insulating films of Examples 1 to 10 and Comparative Example 1 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 removed from the nitrogen atmosphere and the temperature increase rate was set to 10 ° C/min. The temperature was raised to 450 ° C at 30 ° C, and the temperature measured when the loss tangent (tan δ) change rate was maximized was taken as the glass transition temperature. In general, when an insulating film is applied to a flexible copper foil substrate, the degree of solder resistance is tested by a Solder Test, and the test condition of the solder test is usually maintained at 300 ° C for 30 seconds. Therefore, in the application of the flexible copper foil substrate, the glass transition temperature of the insulating film is preferably 300 ° C or higher, and the larger the value, the better the thermal stability of the insulating film.

<Measurement of Thermal Cracking Temperature>

First, 0.5 g to 0.8 g of the insulating films of Examples 1 to 10 and Comparative Example 1 were weighed separately to obtain a test film. Next, using a thermogravimetric loss analyzer (Seiko Instrument Inc., manufactured by Seiko Instrument Inc.) Prepared as EXSTAR 6000), measured in a nitrogen atmosphere and a temperature increase rate of 10 ° C / min, the temperature of the film from 30 ° C to 600 ° C, and measured when the film lost 5% by weight The temperature is taken as the thermal cracking temperature. In the industry, in the application of a flexible copper foil substrate, the thermal cracking temperature of the insulating film generally needs to be at least 400 ° C or more, and the larger the value, the better the thermal stability of the insulating film.

As is clear from Table 2, the contents of Examples 1 to 10 were derived from 4, 4 as compared with the insulating film of Comparative Example 1 which did not contain a divalent organic group derived from 4,4'-diaminodicyclohexylmethane. The divalent organic-based insulating film of '-diaminodicyclohexylmethane has a low dielectric constant and dielectric loss. In addition, as is clear from Table 2, the glass transition temperatures of the insulating films of Examples 1 to 10 were between 262 ° C and 352 ° C and the thermal cracking temperature was between 464 ° C and 495 ° C, which shows Example 1 to The insulating film of Example 10 had good thermal stability.

Further, as is clear from Table 2, in comparison with the insulating film of Example 1, Examples 2 to 9 further contained two derived from p-phenylenediamine and/or 4,4'-diaminophenylhydrazinoanilide. The organic film-based insulating film has a low coefficient of thermal expansion. Furthermore, as can be seen from Table 2, the insulating films of Examples 7 to 9 have a dielectric constant between 3.15 and 3.17, a dielectric loss between 0.052 and 0.063, and a thermal expansion coefficient of 28.8 ppm/ Between °C and 31.5ppm/°C, the glass transition temperature is between 285°C and 296°C, and the thermal cracking temperature is between 477°C and 489°C, which shows that the insulating films of Examples 7 to 9 have both low Dielectric constant, low dielectric loss, thermal expansion coefficient similar to copper foil, and high thermal stability.

Further, as is clear from Table 2, the insulating films of Examples 5 and 6 have lower coefficients of thermal expansion than the insulating films of Examples 2 and 3, and the display structure contains derivatives derived from 4, 4'. The divalent organic group of the diaminophenyl phenylaniline has a better ability to regulate the coefficient of thermal expansion than the structure containing a divalent organic group derived from p-phenylenediamine.

Further, although the above properties were not measured for the insulating films of Examples 11 to 12, the results of the measurement of the insulating films of Examples 1 to 10 and Comparative Example 1 should be understood by those having ordinary knowledge in the field. The insulating film of ~12 also had good dielectric properties, and the polyimide film of Example 12 had a lower coefficient of thermal expansion than the insulating film of Example 11.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art without departing from the invention. In the spirit and scope, the scope of protection of the present invention is subject to the definition of the appended patent application.

Claims (10)

A polymer comprising at least 25 mol% of the repeating unit represented by Formula 1: Wherein Ar is a tetravalent organic group derived from a tetracarboxylic dianhydride containing an aromatic group; and A is a divalent organic group derived from a diamine containing a cyclohexane group, and the carbon of the divalent organic group The number is 8 to 18, and the number of repeating units represented by Formula 1 is between 10 and 2,000. The polymer according to claim 1, further comprising a repeating unit represented by Formula 3: Where Φ includes Or Φ includes versus . The polymer according to claim 1 or 2, wherein Ar includes and At least one of, and B includes a single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -SO ₂ - or -CO-. The polymer of claim 1, wherein A includes , , , and At least one of them. The polymer of claim 2, wherein Φ comprises and And versus The molar ratio is 9:1 to 1:9. An insulating film comprising the polymer of claim 1 of the patent application. The insulating film according to claim 6, wherein the insulating film has a dielectric constant of 2.8 to 3.5. The insulating film according to claim 6, wherein the insulating film has a dielectric loss of 0.005 to 0.014. A flexible copper foil substrate comprising: a copper foil; and an insulating film disposed on the copper foil, wherein the insulating film is an insulating film according to claim 6 of the patent application. The flexible copper foil substrate according to claim 9, further comprising an adhesive layer disposed between the copper foil and the insulating film.