KR20050113384A - A flexible metal clad laminate film comprising poly(amide-imide) flexible insulating film - Google Patents

Abstract

The present invention relates to a flexible metal thin film laminated film, the flexible metal thin film laminated film according to the present invention is a metal thin film; And a poly (amide-imide) flexible insulating film laminated on the metal thin film surface and formed by photocrosslinking of a photosensitive poly (amide-imide) -based polymer. The flexible metal thin film laminate film of the present invention includes a poly (amide-imide) flexible insulating film formed by photocrosslinking a photosensitive poly (amide-imide) polymer in which a triazine ring having a photoactive side chain is introduced into a main chain, Physical properties such as dimensional stability, heat resistance and dielectric constant are improved, and warpage or kink are minimized.

Description

Flexible metal clad laminate film comprising poly (amide-imide) flexible insulating film

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible metal thin film laminate film comprising a poly (amide-imide) flexible insulating film. In particular, a photosensitive poly (amide-imide) polymer in which a triazine ring having a photoactive side chain is introduced into a main chain is photocrosslinked. It relates to a flexible metal thin film laminated film comprising a poly (amide-imide) resin formed as a flexible insulating film.

Recently, due to the trend of miniaturization, high integration, simplicity, and high performance of the electronics, flexible circuit boards, which have thin and free bendability and light characteristics, have been in the spotlight. It is used as a negative.

The flexible metal thin film laminate film is manufactured in a form in which a flexible base film and a conductive metal thin film made of copper or aluminum are laminated, and an adhesive may be used between the flexible base film and the conductive metal thin film. That is, a three-layer structure laminated with a base film-adhesive-metal thin film or a repeated structure, or a two-layer structure made of a base film-metal thin film without an adhesive or a repeated structure.

As a material of the base film used for the flexible metal thin film laminated film, organic polymer materials such as polyimide, polyamide, polyester, polysulfone, polyetherimide and the like are used to impart specific flexibility. The base film should not only have insulation but also have excellent durability against high temperature conditions and chemicals used in the process, and should have physical properties such as dimensional stability, heat resistance, dielectric constant, high mechanical strength, solvent resistance, and solder stability.

By the way, conventionally used base film is good in flexibility, but the coefficient of linear expansion is large. Therefore, the flexible metal thin film laminate film using the same as a base film has a problem that warpage or twisting tends to occur, and physical properties such as dimensional stability, heat resistance, and dielectric constant do not reach a desired level.

Therefore, the technical problem to be achieved by the present invention is to solve the above problems, poly (amide-) formed by photocrosslinking a photosensitive poly (amide-imide) polymer in which a triazine ring having a photoactive side chain is introduced into the main chain Imide) By laminating a flexible insulating film on a metal thin film, it is to provide a flexible metal thin film laminated film with improved physical properties such as dimensional stability, heat resistance, dielectric constant and minimized warpage or kink.

In order to achieve the above technical problem, the flexible metal thin film laminated film according to the present invention is a metal thin film; And a poly (amide-imide) flexible insulating film laminated on the metal thin film surface and formed by photocrosslinking of a photosensitive poly (amide-imide) -based polymer represented by Formula 1 below. The flexible metal thin film laminate of the present invention is a flexible insulating film of a poly (amide-imide) resin formed by photocrosslinking reaction of a photosensitive poly (amide-imide) -based polymer in which a triazine ring having a photoactive side chain is introduced into the main chain. By using it as a material, the physical properties such as dimensional stability, heat resistance, dielectric constant is improved, and warpage or twisting phenomenon is minimized.

In Formula 1, m + n = 1, 0 ≦ m ≦ 1, and 0 ≦ n ≦ 1, and R ₁ is each independently selected from the group consisting of (1a) to (4a) of Formula 2 below.

In (1a) of the formula (2), X is any one selected from the group represented by the following formula (3),

In Formula 3, m and n are each 0 to 10.

In (1a) of the formula (2), Y is any one selected from the group represented by the following formula (4).

In Formula 4, 1,2,3,4,5,6,7,8,9 are each independently selected from the group represented by the following formula (5),

In Formula 5, m and n are each 0 to 10, and A, B, C, D, and E are each independently selected from the group consisting of H, F, Cl, CN, CF _3, and CH ₃ .

In (2a) and (3a) of Formula 2, n is 0 to 10, 1,2,3,4,5 are each independently selected from the group represented by the following formula (6),

In Formula 6, m and n are each 0 to 10, and A, B, C, D, and E are each independently selected from the group consisting of H, F, Cl, CN, CF _3, and CH ₃ .

In (4a) of the formula (2), Y is any one selected from the group represented by the following formula (7),

In Formula 7 n is 0 to 10.

In (4a) of the formula (2), 1 and 2 are each independently selected from the group represented by the following formula (8),

In Formula 8, A is any one selected from the group consisting of H, F, CH ₃ , CF _3, and CN.

On the other hand, the imide bond in the formula (1) is obtained by the reaction of the amine and the acid dianhydride, the general form of the reaction is shown in the following scheme 1.

In addition, the amide bond in the formula (1) is obtained by the reaction of the amine and the carboxylic acid, the general form of the reaction is shown in the following scheme 2.

R ₂ and R ₃ in Formula 1 are each independently derived from any one amine selected from the group consisting of Formula 9,

M and n are each 0-10.

In Formula 1, R ₄ is derived from any one acid dianhydride selected from the group represented by Formula 10 below.

In Formula 1, R ₅ is any one selected from the group represented by Formula 11,

In Formula 11, m and n are each 0 to 10.

When a substituent of a ring structure such as a benzene ring is used to penetrate the ring in the chemical formula used herein, it means that the substituent may be substituted at any carbon position of the ring which is not substituted with another substituent. That is, in the relationship with a substituent substituted at a predetermined position, it indicates that it can be substituted at any position such as ortho, meta, para, and the like.

Hereinafter, the present invention will be described in detail.

In the flexible metal thin film laminate film according to the present invention, a poly (amide-imide) formed by photocrosslinking of the photosensitive poly (amide-imide) polymer represented by Chemical Formula 1 is used as a material of the flexible base film.

Referring to the formula (1), the triazine ring having a photoactive side chain is introduced into the main chain in the photosensitive poly (amide-imide) -based polymer. The triazine ring is a hexagonal aromatic compound, which contains three nitrogen atoms, and has an excellent ability to attract electrons. By introducing such a triazine ring into the main chain, physical properties such as heat resistance and dielectric constant of the polymer resin are improved, and photoreaction occurring in the photoactive side chain is promoted.

R _{1, which} is a photoactive side chain of the triazine ring, is composed of cinnamate, coumarin, chalcone, maleimide derivative, and the like, as shown in Formula 2. Such side chains are crosslinked due to cycloaddition between them by light such as ultraviolet rays. Examples of photocrosslinking reactions that can occur between these side chains are shown below.

   As described above, the flexible metal thin film laminate film of the present invention is a film prepared using the photosensitive poly (amide-imide) polymer represented by Chemical Formula 1 using poly (amide-imide) formed through the photocrosslinking reaction described above. Is used as the flexible insulating film. The poly (amide-imide) flexible insulating film provided in the flexible metal thin film laminate film of the present invention is improved in dimensional stability by using a material crosslinked with a poly (amide-imide) polymer, so that phenomena such as warpage and twisting may be prevented. Not only is it minimized, it is also excellent in physical properties such as heat resistance, dimensional stability, dielectric constant.

In the flexible metal thin film laminate according to the present invention, the number average molecular weight of the poly (amide-imide) polymer compound represented by the formula (1) may be about 1000 to 1000000, such poly (amide-imide) The poly (amide-imide) flexible insulating film formed by photocrosslinking of the polymer may be prepared, for example, in a thickness of 1 nm to 10 cm.

The above-described flexible insulating film is laminated on the surface of the metal thin film to produce a flexible metal thin film laminated film. If necessary, an adhesive layer may be further formed between the metal thin film and the flexible insulating film. As a material of the metal thin film used in the flexible metal thin film laminate according to the present invention, metals such as copper, platinum, gold, silver, and aluminum may be used. Particularly, copper having excellent cost performance is more preferable. Typically, the metal thin film is manufactured to a thickness of 0.1 ~ 500㎛.

Flexible metal thin film laminate film according to the present invention can be prepared by the following method.

First, a photosensitive poly (amide-imide) polymer solution is applied to a metal thin film. In this case, the photosensitive poly (amide-imide) polymer solution may further dissolve the poly (amide-imide) polymer commonly used as a material of the flexible insulating film. Subsequently, the solvent is removed and then photocrosslinked to obtain a flexible metal thin film laminate according to the present invention.

The manufacturing method in the case of forming an adhesive layer between a metal thin film and a poly (amide-imide) flexible insulating film is as follows.

First, the solvent is removed by applying a poly (amide-imide) polymer solution to a support such as a glass plate. The poly (amide-imide) polymer is then photocrosslinked to obtain a poly (amide-imide) flexible film. Then, the flexible film is peeled from the support, and the adhesive film is bonded to the metal thin film using an adhesive to prepare a flexible metal thin film laminated film consisting of three layers of a metal thin film-adhesive layer-poly (amide-imide) base film.

In the latter method, an adhesive is mainly an acrylic or silicone adhesive, which causes process problems such as lack of heat resistance and thermal stress due to a difference in coefficient of thermal expansion. Therefore, it is preferable to use the former method which does not use an adhesive separately.

Hereinafter, examples will be described in detail to help understand the present invention. However, embodiments according to the present invention can be modified in many different forms, the scope of the invention should not be construed as limited to the following examples. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

Preparation Example: Preparation of Photosensitive Poly (amide-imide) Polymer

Preparation Example 1 Preparation of Photosensitive Poly (amide-imide) Polymer Having Cinnamate Photoactive Side Chain

(1) Modification of Triazine Rings

27.1 g of 4- (2-tetrahydropyranylmethoxy) bromobenzene was dissolved in 250 ml of anhydrous tetrahydrofuran in a nitrogen-filled three-necked flask and reacted with 3 g of magnesium for 24 hours. The solution was reacted for 12 hours in a nitrogen-filled three-necked flask with 18.4 g of cyanuric chloride dissolved in 200 ml of anhydrous tetrahydrofuran while slowly dropping at -20 ° C. After the reaction was terminated, the reaction solution was dried under reduced pressure at room temperature to remove tetrahydrofuran, and then dissolved in ethyl acetate. The solution was mixed with a basic aqueous solution to extract impurities with vigorous stirring, the aqueous phase was separated and removed, and the ethyl acetate was removed under reduced pressure at room temperature. The solvent was removed and the remaining solid material was recrystallized in normal hexane to obtain 30 g of 2- (4- (2-tetrahydropyranylmethoxy) phenyl) -4,6-dichloro-1,3,5-triazine.

(2) hydroxy functional group introduced into triazine ring

Preparation Example 1 34.0 g of the material obtained by the method of (1) was put in a round bottom flask and dissolved in 300 ml of tetrahydrofuran, and 0.3 g of pyridinium paratoluenesulfonate was further added, followed by addition of 50 ml of ethanol for 24 hours. Reacted. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and the remaining solids were dissolved in methylene chloride, and then mixed with distilled water in a separatory funnel to extract the impurities twice. Calcium chloride was added to the methylene chloride solution to remove moisture, and the solvent was removed by distillation under reduced pressure. This solid phase was recrystallized from a mixed solution of methylene chloride and normal hexane to give 20.6 g of 2- (4-hydroxyphenyl) -4,6-dichloro-1,3,5-triazine.

(3) Synthesis of triazine ring with cinnamate side chain

Preparation Example 1 (2) 25.6 g of the triazine obtained by the method in a round bottom flask filled with nitrogen, 200 ml of anhydrous tetrahydrofuran was added to dissolve. After adding 15.2 g of triethylamine to the solution and lowering the temperature to -5 ° C, 100 ml of anhydrous tetrahydrofuran was added to 25 g of cinnamoyl chloride, and the diluted cinnamoyl chloride solution was slowly added dropwise to react for 12 hours. After the reaction was completed, the reaction solution was distilled under reduced pressure to remove tetrahydrofuran, which was dissolved in methylene chloride and passed through a filter filled with silica gel, followed by distillation under reduced pressure to remove the solvent. Finally, the mixture was recrystallized from a mixed solvent of methylene chloride and normal hexane and filtered under reduced pressure. The obtained solid substance was vacuum dried to obtain 35.1 g of triazine having cinnamate side chains.

(4) Synthesis of Triazine Monomer Having Two Amine Functions

Preparation Example 1 (3) 38.6 g of triazine obtained by the method was put in a round bottom flask and dissolved in 400 ml of chloroform. 32.8 g of 4-aminophenol and 12 g of sodium hydroxide were dissolved in 300 ml of distilled water dissolved in 3 g of cetyltrimethylammonium bromide, mixed with the previous triazine solution, and reacted vigorously for 24 hours. After completion of the reaction, the organic solution phase was separated, transferred to a separatory funnel, washed three times with distilled water to extract impurities, and then water was removed with calcium chloride. The water solution was distilled under reduced pressure to remove chloroform and recrystallized from a mixed solution of methylene chloride and normal hexane. The precipitated crystals were filtered under reduced pressure and dried in vacuo to yield 49.2 g of triazine monomer.

(5) Polymerization of Photosensitive Polymer Having Cinnamate Photoactive Side Chain

 Preparation Example 1 53.156 g of the triazine monomer obtained by the method of (4) was placed in a round bottom flask filled with nitrogen and dissolved in 400 ml of anhydrous tetrahydrofuran. 20.238 g of triethylamine was added to this solution. After dissolving 10.15 g of terephthaloyl chloride in 100 ml of anhydrous tetrahydrofuran, the mixture was stirred vigorously while being slowly added dropwise to the solution containing the triazine monomer and triethylamine, and allowed to react for 6 hours. The solution which melt | dissolved the solution which melt | dissolved 10.9 g of 1,2,4, 5- benzene tetracarboxylic dianhydride in 100 ml of N-methylpyrrolidone was dripped at this solution, and it was made to react for 6 hours. After completion of the reaction, the reaction solution was slowly poured into methanol, precipitated and filtered, and the precipitate was dried in vacuo. The obtained precipitate was again dissolved in tetrahydrofuran and precipitated in methanol twice, followed by vacuum drying to finally synthesize 40.1 g of a poly (amide-imide) copolymer polymer having triazine ring having a cinnamate photoactive side chain. .

Preparation Example 2 Preparation of Photosensitive Poly (amide-imide) Polymer Having a Calcon Photoactive Side Chain

(1) Synthesis of Chalcone Photosensitive Functional Group

10 g of 4-methoxychalcone and 2.05 g of sodium cyanide were dissolved in 100 ml of dimethyl sulfoxide and allowed to react for 24 hours. After completion of the reaction, the reaction solution was mixed with chloroform and stirred with distilled water to extract impurities. After removing the aqueous phase, the chloroform was removed under reduced pressure at room temperature. The remaining solid phase was recrystallized in methanol and dried in vacuo at 40 ° C. to give 19.7 g of 4-hydroxychalcone which could serve as a side chain for the photoreaction.

(2) Introduction of Chalcone Photosensitive Functional Groups into Triazine Rings

Preparation Example 2 23.8 g of 4-hydroxychalcone synthesized in the method of (1) was placed in a round bottom flask filled with nitrogen and dissolved in 240 ml of anhydrous tetrahydrofuran. 2.4 g of sodium hydride (NaH) was added thereto and allowed to react at room temperature for 6 hours. The solution obtained by the above-mentioned reaction was reacted for 24 hours with vigorous stirring while slowly dropping 18.4 g of cyanuric chloride in 200 ml of anhydrous tetrahydrofuran while slowly dropping at -5 占 폚. After completion of the reaction, distillation under reduced pressure was carried out to remove tetrahydrofuran, and the obtained solid was dissolved in chloroform again. The solution was washed three times with distilled water in a separatory funnel to extract impurities, and then water was removed with calcium chloride. The solution was distilled under reduced pressure again to remove chloroform and recrystallized with a mixed solvent of methylene chloride and normal hexane. The obtained material was filtered under reduced pressure and dried under vacuum to obtain 31.3 g of a triazine having a chalcone photosensitive functional group.

(3) Synthesis of Triazine Monomer Having Two Amine Functions

Preparation Example 2 38.6 g of a triazine having a chalcon photosensitive functional group obtained by the method of (2) was put in a round bottom flask and dissolved in 300 ml of chloroform. 32.8 g of 4-aminophenol and 12 g of sodium hydroxide were dissolved in 300 ml of distilled water in which 3 g of cetyltrimethylammonium bromide was dissolved, mixed with the triazine solution prepared above, and reacted vigorously for 24 hours. After completion of the reaction, the organic solution phase was separated, transferred to a separatory funnel, washed three times with distilled water to extract impurities, and then water was removed with calcium chloride. The water-removed solution was distilled under reduced pressure to remove chloroform, an organic solvent, and then recrystallized from a mixed solvent of methylene chloride and normal hexane. The precipitated crystals were filtered under reduced pressure and dried in vacuo to give 48.7 g of a triazine monomer.

(4) Polymerization of Photosensitive Poly (amide-imide) Polymer Having a Calcon Photosensitive Functional Group

53.15 g of the triazine monomer obtained by the method of Preparation Example 2 (3) was placed in a round bottom flask filled with nitrogen and dissolved in 400 ml of tetrahydrofuran from which water was removed. 20.24 g of triethylamine was added to this solution. 10.15 g of terephthaloyl chloride was dissolved in 100 ml of anhydrous tetrahydrofuran, and the mixture was reacted for 6 hours by vigorous stirring while slowly dropping the solution of the previous triazine monomer and triethyl amine. The solution which melt | dissolved the solution which melt | dissolved 10.9 g of 1,2,4, 5- benzene tetracarboxylic dianhydride in 100 ml of N-methylpyrrolidone was dripped at this solution, and it was made to react for 6 hours. After completion of the reaction, the reaction solution was slowly poured into methanol, precipitated and filtered, and the precipitate was dried in vacuo. The obtained precipitate was again dissolved in tetrahydrofuran, precipitated in methanol twice, and then vacuum dried to finally introduce a triazine ring having a chalcone photoactive side chain into the main chain. g was synthesized.

Preparation Example 3 Preparation of Photosensitive Poly (amide-imide) Polymer Having a Coumarin Photoactive Side Chain

(1) Introduction of coumarin photosensitive functional group

16.2 g of 7-hydroxycoumarin and 2.4 g of sodium hydride (NaH) were placed in a round-bottomed flask filled with nitrogen, dissolved in 160 ml of anhydrous tetrahydrofuran, and stirred vigorously for 6 hours. This solution was reacted for 24 hours with vigorous stirring while slowly dropping 18.4 g of cyanuric chloride in 200 ml of anhydrous tetrahydrofuran at −5 ° C. After completion of the reaction, distillation under reduced pressure was carried out to remove tetrahydrofuran, and the obtained solid was dissolved in chloroform again. The solution was washed three times with distilled water in a separatory funnel to extract impurities, and then water was removed with calcium chloride. The solution was distilled under reduced pressure again to remove chloroform and recrystallized with a mixed solvent of methylene chloride and normal nucleic acid. The obtained material was filtered under reduced pressure and then vacuum dried to obtain 28.2 g of triazine having a coumarin photosensitive functional group.

(2) Synthesis of Triazine Monomer Having Two Amine Functions

 Preparation Example 3 31.1 g of a triazine having a coumarin photosensitive functional group obtained by the method of (1) was placed in a round bottom flask and dissolved in 300 ml of chloroform. 32.8 g of 4-aminophenol and 12 g of sodium hydroxide were dissolved in 300 ml of distilled water in which 3 g of cetyltrimethylammonium bromide was dissolved, mixed with the triazine solution prepared above, and reacted vigorously for 24 hours. After completion of the reaction, the organic solution phase was separated, transferred to a separatory funnel, washed three times with distilled water to extract impurities, and then water was removed with calcium chloride. The water-removed solution was distilled under reduced pressure to remove chloroform, an organic solvent, and then recrystallized from a mixed solvent of methylene chloride and normal hexane. The precipitated crystals were filtered under reduced pressure and dried in vacuo to give 41.6 g of a triazine monomer.

(3) Polymerization of Photosensitive Polymers Having Coumarin Photoactive Side Chains

45.54 g of the triazine monomer obtained by the method of Preparation Example 3 (2) was placed in a round bottom flask filled with nitrogen and dissolved in 400 ml of anhydrous tetrahydrofuran. 20.24 g of triethylamine was added to this solution. After dissolving 10.15 g of terephthaloyl chloride in 100 ml of anhydrous tetrahydrofuran, the mixture was reacted for 6 hours by vigorous stirring while slowly dropping the solution of the previous triazine monomer and triethylamine. The solution which melt | dissolved the solution which melt | dissolved 10.9 g of 1,2,4, 5- benzene tetracarboxylic dianhydride in 100 ml of N-methylpyrrolidone was dripped at this solution, and it was made to react for 6 hours. After the completion of the reaction, the reaction solution was slowly poured into methanol to precipitate, and the precipitate was filtered and dried in vacuo. The obtained precipitate was again dissolved in tetrahydrofuran and precipitated in methanol twice. Vacuum drying was carried out to obtain 26.7 g of a poly (amide-imide) copolymer polymer having a triazine ring having a coumarin photoactive side chain finally introduced into the main chain. Synthesized.

Example 1 Preparation of Flexible Metal Thin Film Laminated Film

The photosensitive polymer prepared in Preparation Example 1 was dissolved in NMP (N-methylpyrrolidone), an organic solvent to have a viscosity of 20000 cps, to form a polymer solution, and then 25 μm in a 18 μm thick copper thin film with a 1 m / min coater. The resin layer was coated to have a thickness of, and the solvent was removed at 200 ° C., and then irradiated with an ultraviolet lamp having a light amount of 600 W / inch to induce a photochemical reaction.

Examples 2 and 3: Preparation of flexible metal thin film laminated film

A flexible metal thin film laminate film was manufactured in the same manner as in Example 1, except that the photosensitive polymer obtained in Preparation Example 2 (Example 2) and Preparation Example 3 (Example 3) was used instead of the photosensitive polymer obtained in Preparation Example 1. It was.

Physical properties of the flexible metal thin film laminate films prepared in Examples 1 to 3 were measured, and the results are shown in Table 1.

In addition, the reflow resistance (85 ° C., 60% RH, 168 hr. + Reflow) of the flexible copper thin film laminate films prepared in Examples 1 to 3 was measured, and the results are shown in Table 2.

As shown in Table 1 and Table 2, the flexible metal thin film laminated film according to the present invention exhibits excellent dimensional stability, heat resistance, dielectric constant, etc., in particular, it can be seen that there is almost no warpage or twisting phenomenon.

As described above, the poly (amide-imide) obtained by the photocrosslinking reaction of the photosensitive poly (amide-imide) polymer in which a triazine ring having a photoactive side chain is introduced into the main chain according to the present invention is a flexible insulating film. The flexible metal thin film laminated film used as the material showed excellent dimensional stability, heat resistance, dielectric constant, and almost no warping or twisting occurred. Therefore, the flexible metal thin film laminate according to the present invention can be very usefully used in the electronics industry such as small electronics.

Claims (6)

(a) a metal thin film; And (b) a flexible metal comprising: a poly (amide-imide) flexible insulating film laminated on the metal thin film surface and formed by photocrosslinking of a photosensitive poly (amide-imide) -based polymer represented by Formula 1 below; Thin film laminated film. <Formula 1> In Formula 1, m + n = 1, 0 ≤ m ≤ 1 and 0 ≤ n ≤ 1, R ₁ is each independently selected from the group consisting of (1a) to (4a) of the formula (2) , <Formula 2> In (1a) of the formula (2), X is any one selected from the group represented by the following formula (3), <Formula 3> In Formula 3, m and n are each 0 to 10, In (1a) of the formula (2), Y is one selected from the group represented by the following formula (4), <Formula 4> In Formula 4, 1,2,3,4,5,6,7,8,9 are each independently selected from the group represented by the following formula (5), <Formula 5> In Formula 5, m and n are each 0 to 10, and A, B, C, D, and E are each independently selected from the group consisting of H, F, Cl, CN, CF _3, and CH ₃ . , In (2a) and (3a) of Formula 2, n is 0 to 10, 1,2,3,4,5 are each independently selected from the following Formula 6, <Formula 6> In Formula 6, m and n are each 0 to 10, and A, B, C, D, and E are each independently selected from the group consisting of H, F, Cl, CN, CF _3, and CH ₃ . , In (4a) of the formula (2), Y is any one selected from the group represented by the following formula (7), <Formula 7> In Formula 7 n is 0 to 10, In (4a) of the formula (2), 1 and 2 are each independently selected from the group represented by the following formula (8), <Formula 8> In Formula 8, A is any one selected from the group consisting of H, F, CH ₃ , CF ₃ and CN, In Formula 1, R ₂ and R ₃ are each independently derived from any one amine selected from the group represented by Formula 9, <Formula 9> In Formula 9, m and n are each 0 to 10, In Formula 1, R ₄ is derived from any one acid dianhydride selected from the group represented by Formula 10, <Formula 10> In Formula 1, R ₅ is any one selected from the group represented by Formula 11, <Formula 11> In Formula 11, m and n are each 0 to 10. The flexible metal thin film laminate film according to claim 1, wherein the photosensitive poly (amide-imide) polymer has a number average molecular weight (Mn) of 1000 to 1000000. The flexible metal thin film laminate film of claim 1, wherein the metal thin film is any one selected from the group consisting of copper, platinum, gold, silver, and aluminum. The flexible metal thin film laminate film according to claim 1, wherein the metal thin film has a thickness of 0.1 to 500 µm. The flexible metal thin film laminate film according to claim 1, wherein an adhesive layer is further formed between the metal thin film and the poly (amide-imide) flexible insulating film. The flexible metal thin film laminate film according to any one of claims 1 to 5, wherein the poly (amide-imide) flexible insulating film has a thickness of 1 nm to 10 cm.