KR100586108B1 - A flexible metal clad laminate film comprising polythioether 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 polythioether flexible insulating film laminated on the metal thin film surface and formed by photocrosslinking of the photosensitive polythioether polymer. The flexible metal thin film laminate film of the present invention includes a polythioether flexible insulating film formed by photocrosslinking a photosensitive polythioether polymer in which a triazine ring having a photoactive side chain is introduced into a main chain, thereby providing dimensional stability, heat resistance, dielectric constant, and the like. Physical properties are improved and warping or twisting are minimized.

Flexible metal thin film laminated film, photosensitive, polythioether, triazine, photocrosslinking reaction

Description

A flexible metal clad laminate film comprising polythioether flexible insulating film

The present invention relates to a flexible metal thin film laminate film including a polythioether flexible insulating film, and particularly, to a polythioether resin formed by photocrosslinking a photosensitive polythioether polymer having a triazine ring having a photoactive side chain introduced into a main chain thereof. It relates to a flexible metal thin film laminated film included as an 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, a polythioether flexible insulating film formed by photocrosslinking a photosensitive polythioether polymer in which a triazine ring having a photoactive side chain is introduced into the main chain metal The present invention provides a flexible metal thin film laminate film in which physical properties such as dimensional stability, heat resistance, and dielectric constant are improved, and warpage or kink are minimized by laminating to a thin film.

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 polythioether flexible insulating film laminated on the metal thin film surface and formed by photocrosslinking of a photosensitive polythioether-based polymer represented by Formula 1 below. The flexible metal thin film laminate film of the present invention has a dimensional stability by using a polythioether resin formed by the photocrosslinking reaction of a photosensitive polythioether polymer having a triazine ring having a photoactive side chain in the main chain, Physical properties such as heat resistance and dielectric constant are improved, and warpage or kinks are 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, and 1,2,3,4,5 are each independently selected from the group represented by Formula 6 below,

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 thioether bond in the formula (1) is obtained by the reaction of a halide and thiol (thiol), the general form of the reaction is shown in the following scheme 1.

R ₂ and R ₃ in Formula 1 are each independently selected from the group consisting of the following Formula 9,

delete

In Formula 9, m and n are each 0 to 10, and A and 1,2,3,4,5,6,7,8 are each independently of each other H, F, Cl, CN, CF ₃ , and CH _It is any one selected from the group which consists of _three .

R ₄ and R ₅ in Formula 1 are each independently of one another. Any one selected from the group represented by the following formula (10).

In Formula 10, m and n are each 0 to 10, and A and 1,2,3,4,5,6,7,8 are each independently of each other H, F, Cl, CN, CF ₃ , and CH Any one selected from the group consisting of ₃ ;

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 polythioether formed by photocrosslinking of the photosensitive polythioether polymer represented by Chemical Formula 1 is used as a material of the flexible base film.

Referring to Formula 1, the triazine ring having a photoactive side chain is introduced into the main chain in the photosensitive polythioether 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, in the flexible metal thin film laminate film of the present invention, the photosensitive polythioether polymer represented by Chemical Formula 1 uses a film prepared by using the polythioether formed through the photocrosslinking reaction as the flexible insulating film. The polythioether flexible insulating film provided in the flexible metal thin film laminate film of the present invention improves the dimensional stability by using a crosslinked material of the polythioether polymer, thereby minimizing the phenomenon of warpage and twisting, as well as heat resistance and dimensions. It also has excellent physical properties such as stability and dielectric constant.

In the flexible metal thin film laminate according to the present invention, the number average molecular weight of the polythioether polymer compound represented by Formula 1 may be about 1000 to 1000000, and such a polythioether polymer is formed by photocrosslinking reaction. The polythioether flexible insulating film may be produced, for example, in a thickness of 1 nm to 125 μm.

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 polythioether polymer solution is applied to a metal thin film. In this case, the photosensitive polythioether polymer solution may further dissolve the polythioether 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 the metal thin film and the polythioether flexible insulating film is as follows.

First, a polythioether polymer solution is applied to a support such as a glass plate to remove a solvent. Next, the polythioether polymer is photocrosslinked to obtain a polythioether flexible film. Then, the flexible film is peeled off from the support, and the adhesive film is bonded to the metal thin film using an adhesive to prepare a flexible metal thin film laminate film consisting of three layers of a metal thin film-adhesive layer-polythioether 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 Polythioether Polymer

Preparation Example 1 Preparation of Photosensitive Polythioether Polymer Having Cinnamate Photoactive Side Chain

(1) Modification of Triazine Rings

25.7 g of 4- (2-tetrahydropyranyloxy) bromobenzene was dissolved in a nitrogen-filled three-necked flask with 250 ml of dehydrated tetrahydrofuran and reacted with 3 g of magnesium for 24 hours. The solution was reacted for 12 hours at -20 ° C while slowly dropwise adding a solution of 18.4 g of cyanuric chloride to 200 ml of anhydrous tetrahydrofuran in a nitrogen-filled three-necked flask. After the reaction was terminated, the reaction solution was decompressed at room temperature to remove tetrahydrofuran and dissolved in ethyl acetate. The solution was mixed with the basic aqueous solution, the impurities were extracted 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 give 30.1 g of 2- (4- (2-tetrahydropyranyloxy) phenyl) -4,6-dichloro-1,3,5-triazine. .

(2) Introduction of hydroxy functional groups to triazine ring

Preparation Example 1 32.6 g of the material obtained by the method of (1) was put in a round bottom flask again and dissolved in 300 ml of tetrahydrofuran, followed by adding 0.3 g of pyridinium paratoluenesulfonate, and then adding 50 ml of ethanol to react for 24 hours. Was done. After completion of the reaction, the solvents were 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 impurities twice. Calcium chloride was added to the methylene chloride solution to remove water and distilled under reduced pressure to remove the solvent. This solid phase was recrystallized in a mixed solvent of methylene chloride and normal hexane to give 20.5 g of 2- (4-hydroxyphenyl) -4,6-dichloro-1,3,5-triazine.

(3) Synthesis of triazine ring with cinnamate side chain

24.2 g of triazine obtained by the method of Preparation Example 1 (2) was put into a round bottom flask filled with nitrogen, and 200 ml of anhydrous tetrahydrofuran was added to dissolve it. 15.2 g of triethylamine was added to the solution, the temperature was lowered to -5 ° C, and 100 ml of anhydrous tetrahydrofuran was added to 25 g of cinnamoyl chloride. The diluted cinnamoyl chloride solution was slowly added dropwise and stirred for 12 hours to react. . After completion of the reaction, the reaction solution was distilled under reduced pressure to remove tetrahydrofuran, the remaining solid was dissolved in methylene chloride, passed through a filter filled with silica gel, and then distilled under reduced pressure to remove the solvent. Finally, after recrystallization in a 1: 1 mixed solvent of methylene chloride and normal hexane, and filtered under reduced pressure. The obtained solid substance was vacuum dried to obtain 30.2 g of triazine having cinnamate side chains.

(4) Synthesis of Triazine Monomer Having Two Halide Functional Groups

Preparation Example 1 (3) 37.2g of the triazine obtained by the method in a round bottom flask was dissolved in 400ml of chloroform. 25.6 g of 4-chlorophenol and 8 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 50.3 g of a triazine monomer.

(5) Polymerization of polythioether photosensitive polymer having cinnamate photosensitive functional group

Preparation Example 1 55.3 g of the triazine monomer obtained by the method of (4) was put in a round bottom flask filled with nitrogen and dissolved in 600 ml of nitrobenzene. 14.2 g of 1,4-phenyldithiol, 8 g of sodium hydroxide, and 0.3 g of cetyltrimethylammonium bromide are dissolved in 100 ml of water, mixed with a nitrobenzene solution in which the triazine monomer is dissolved, followed by vigorous stirring for 24 hours. I was. 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 synthesize 35.9 g of a photosensitive polythioether polymer having a triazine ring having a cinnamate photoactive side chain finally introduced into the main chain. .

Preparation Example 2: Photosensitive polythioether polymer having a chalcone photosensitive functional group

(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 reacted for 24 hours. After completion of the reaction, the reaction solution was mixed with chloroform and stirred with distilled water to extract impurities. The aqueous phase was removed and then decompressed at room temperature to remove chloroform. The remaining solid phase was recrystallized in methanol and dried in vacuo at 40 ° C. to give 20.7 g of 4-hydroxychalcone which could function as a side chain for the photoreaction.

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

Preparation Example 2 (23.8g) of 4-hydroxychalcone obtained by the method of (1) was put in a round bottom flask filled with nitrogen and dissolved in 240ml of anhydrous tetrahydrofuran. 2.4 g of sodium hydride (NaH) was added thereto and allowed to react at room temperature for 6 hours. 18.4 g of cyanuric chloride was dissolved in 200 ml of anhydrous tetrahydrofuran, and the solution was reacted vigorously with vigorous stirring at −5 ° C. for 24 hours. 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 then vacuum dried to obtain 31.6 g of triazine having a chalcone photosensitive functional group.

(3) Synthesis of Triazine Monomer Having Two Halide Functional Groups

Preparation Example 2 38.6 g of a triazine having a chalcone photosensitive functional group obtained by the method of (2) was dissolved in 400 ml of chloroform. 25.6 g of 4-chlorophenol and 8 g of sodium hydroxide were dissolved in 300 ml of distilled water in which 3 g of cetyltrimethylammonium bromide was dissolved, 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-free solution was distilled under reduced pressure to remove chloroform, an organic solvent, and 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 50.2 g of a triazine monomer.

 (4) Polymerization of Polythioether Photosensitive Polymer Having Chalcon Photosensitive Functional Group

Preparation Example 2 56.7 g of the triazine monomer obtained by the method of (3) was placed in a round bottom flask and dissolved in 600 ml of nitrobenzene. 14.2 g of 1,4-phenyldithiol, 8 g of sodium hydroxide, and 0.3 g of cetyltrimethylammonium bromide were dissolved in 100 ml of water, mixed with a nitrobenzene solution in which the triazine monomer was dissolved, followed by vigorous stirring for 24 hours. I was. After completion of the reaction, the reaction solution was slowly poured into methanol to precipitate 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 synthesize 35.2 g of a photosensitive polythioether polymer having a triazine ring having a chalcone photoactive side chain.

Preparation Example 3: Photosensitive polythioether polymer having a coumarin photosensitive functional group

(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. 18.4 g of cyanuric chloride was added to a round bottom flask, and the solution was dissolved in 200 ml of tetrahydrofuran from which water was removed. After completion of the reaction, distillation under reduced pressure 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 dried in vacuo to give 29.7 g of triazine having a coumarin photosensitive functional group.

(2) Synthesis of Triazine Monomer Having Two Halide Functional Groups

Preparation Example 3 31.1 g of a triazine having a coumarin photosensitive functional group obtained by the method of (1) was dissolved in 400 ml of chloroform. 25.6 g of 4-chlorophenol and 8 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 40.2 g of a triazine monomer.

 (3) Polymerization of polythioether photosensitive polymer having coumarin photosensitive functional group

Preparation Example 3 49.1 g of the triazine monomer obtained by the method of (2) was put in a round bottom flask and dissolved in 600 ml of nitrobenzene. 14.2 g of 1,4-phenyldithiol, 8 g of sodium hydroxide, and 0.3 g of cetyltrimethylammonium bromide were dissolved in 100 ml of water, mixed with a nitrobenzene solution in which the triazine monomer was dissolved, followed by vigorous stirring for 24 hours. I was. 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 then precipitated in methanol twice, followed by vacuum drying to synthesize 37 g of a photosensitive polythioether polymer in which a triazine ring having a coumarin photoactive side chain was finally introduced into the main chain.

Example 1 Preparation of Flexible Metal Thin Film Laminated Film

The photosensitive polymer obtained in Preparation Example 1 was coated to a resin layer having a thickness of 25 μm on an 18 μm thick copper thin film with a coater having a flux of 1 m / min, and an ultraviolet lamp having a light amount of 600 W / inch after removing the solvent at 200 ° C. Was investigated 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 metal 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, a flexible metal thin film laminate using a polythioether obtained by photocrosslinking of a photosensitive polythioether polymer having a triazine ring having a photoactive side chain in the main chain according to the present invention as a material of a flexible insulating film The film showed excellent dimensional stability, heat resistance and dielectric constant, and little 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 thin film laminate film comprising: a polythioether flexible insulating film laminated on the metal thin film surface and formed by photocrosslinking of a photosensitive polythioether polymer represented by the following Chemical Formula 1. <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 any 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 selected from the group represented by Formula 9 below, <Formula 9>

In Formula 9, m and n are each 0 to 10, and A and 1,2,3,4,5,6,7,8 are each independently H, F, Cl, CN, CF ₃ , and CH ₃ Any one selected from the group consisting of, In Formula 1, R ₄ and R ₅ are each independently selected from the group represented by the following Formula 10, <Formula 10>

In Formula 10, m and n are each 0 to 10, and A and 1,2,3,4,5,6,7,8 are each independently H, F, Cl, CN, CF ₃ , and CH ₃ Any one selected from the group consisting of. The flexible metal thin film laminate film according to claim 1, wherein the photosensitive polythioether 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 polythioether flexible insulating film. delete