TWI816041B - Polyimide composition, polyimide film and polyimide copper clad laminate - Google Patents

Abstract

A polyimide composition is formed by polymerizing dianhydride monomer and diamine monomer. The dianhydride monomer has an asymmetric structure. The dianhydride monomer has a first polar group and a side chain group. The first polar group is an ester group. The molecular structure of the side chain group is:

Description

Polyimide composition, polyimide film and polyimide copper-clad laminate

The invention relates to a polyimide composition, a polyimide film obtained by coating and baking the polyimide composition, and a polyimide copper-clad laminate using the polyimide film.

In recent years, printed circuit boards have been widely used in various electronic products. At present, printed circuit boards are generally made of copper-clad laminates as base materials. Among them, the copper-clad laminate includes copper foil, a polyimide film, and an adhesive layer located between the copper foil and the polyimide film for bonding the copper foil and the polyimide film together.

During the manufacturing process of the circuit board, part of the copper foil bonded to the surface of the polyimide film will be etched away, leaving the polyimide film in this area exposed without being bonded to the copper foil. This will cause problems during circuit board installation and other processes. A CCD camera is used to see through the polyimide film without copper foil to accurately position the components. Therefore, the polyimide film without copper foil is required to have excellent light transmittance.

However, polyimide films in the prior art mostly appear brown or yellow. The structure of polyimide contains groups such as benzene ring (C=C), which causes the π electron conjugation effect on the conjugated benzene ring and the interaction between molecules. The internal charge transfer CTC is generated, causing the polyimide film to have strong absorption in the visible light region, making the polyimide film opaque.

In view of this, it is necessary to provide a polyimide composition that can weaken the CTC effect of intermolecular and intramolecular charge transfer and thereby have better transparency.

In addition, it is also necessary to provide a polyimide film prepared by coating and baking the polyimide composition to undergo a cyclization reaction.

In addition, it is also necessary to provide a polyimide copper-clad laminate made by using the polyimide film.

；所述二胺單體為非對稱結構且具有第二極性基團，其中，所述第二極性基團為氮雜環、醚基中的一種或兩種。 A polyimide composition, which is polymerized by a dianhydride monomer and a diamine monomer. The dianhydride monomer has an asymmetric structure. The dianhydride monomer has a first polar group and a side chain group. , wherein the first polar group is an ester group, and the molecular structural formula of the side chain group is

; The diamine monomer has an asymmetric structure and has a second polar group, wherein the second polar group is one or both of a nitrogen heterocycle and an ether group.

的環十二烷-1,1-二基雙(2-甲基-4,1-亞苯基)雙(1,3-二氧代-1,3-二氫異苯並呋喃-5-羧酸乙酯)。 Further, the dianhydride has a molecular structural formula of

Cyclodecane-1,1-diylbis(2-methyl-4,1-phenylene)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5- ethyl carboxylate).

，所述4,4'-二氨基-2,2'-聯吡啶的分子結構式是：

，所述1,3-雙(3-氨基苯氧基)苯的分子結構式是：

，所述2,6-二氨基吡啶的分子結構式是：

，所述2-(4-氨基苯基)-5-氨基苯並咪唑的分子結構式是：

。 Further, the diamine monomer is 3,5-diamino-1,2,4-triazole, 4,4'-diamino-2,2'-bipyridine, 1,3-bis(3 -Aminophenoxy)benzene, at least one of 2,6-diaminopyridine and 2-(4-aminophenyl)-5-aminobenzimidazole; wherein, the 3,5-diamino-1, The molecular structural formula of 2,4-triazole is:

, the molecular structural formula of the 4,4'-diamino-2,2'-bipyridine is:

, the molecular structural formula of the 1,3-bis(3-aminophenoxy)benzene is:

, the molecular structural formula of the 2,6-diaminopyridine is:

, the molecular structural formula of the 2-(4-aminophenyl)-5-aminobenzimidazole is:

.

Further, the molar ratio of the dianhydride monomer to the diamine monomer is: 0.8-1.2.

Further, the polyimide composition also contains a solvent, and in the polyimide composition, the weight percentage of the solvent is 70%-85%.

Further, the solvent is at least one of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and dimethylstyrene.

，所述聚醯亞胺膜為非對稱結構。 A polyimide film, the polyimide film contains polar groups and side chain groups, the polar groups are one or two of nitrogen heterocycles and ether groups, and the side chain groups The molecular structural formula of the group is:

, the polyimide film has an asymmetric structure.

；所述二胺單體為非對稱結構且具有第二極性基團，其中，所述第二極性基團為氮雜環、醚基中的一種或兩種。 Further, the polyimide film is generated by coating and baking a dianhydride monomer and a diamine monomer, the dianhydride monomer has an asymmetric structure, and the dianhydride monomer has a first polar group and Side chain group, wherein the first polar group is an ester group, and the molecular structural formula of the side chain group is

; The diamine monomer has an asymmetric structure and has a second polar group, wherein the second polar group is one or both of a nitrogen heterocycle and an ether group.

的環十二烷-1,1-二基雙(2-甲基-4,1-亞苯基)雙(1,3-二氧代-1,3-二氫異苯並呋喃-5-羧酸乙酯)；所述二胺單體為3,5-二氨基-1,2,4-三氮唑、4,4'-二氨基-2,2'-聯吡啶、1,3-雙(3-氨基苯氧基)苯、2,6-二氨基吡啶及2-(4-氨基苯基)-5-氨基苯並咪唑中的至少一種；其中，所述3,5-二氨基-1,2,4-三氮唑的分子結構式是：

，所述4,4'-二氨基-2,2'-聯吡啶的分子結構式是：

，所述1,3-雙(3-氨基苯氧基)苯的分子結構式是：

，所述2,6-二氨基吡啶的分子結構式是：

，所述2-(4-氨基苯基)-5-氨基苯並咪唑的分子結構式是：

。 Further, the dianhydride has a molecular structural formula of

Cyclodecane-1,1-diylbis(2-methyl-4,1-phenylene)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5- Ethyl carboxylate); the diamine monomer is 3,5-diamino-1,2,4-triazole, 4,4'-diamino-2,2'-bipyridine, 1,3- At least one of bis(3-aminophenoxy)benzene, 2,6-diaminopyridine and 2-(4-aminophenyl)-5-aminobenzimidazole; wherein, the 3,5-diamino The molecular structural formula of -1,2,4-triazole is:

, the molecular structural formula of the 4,4'-diamino-2,2'-bipyridine is:

, the molecular structural formula of the 1,3-bis(3-aminophenoxy)benzene is:

, the molecular structural formula of the 2,6-diaminopyridine is:

, the molecular structural formula of the 2-(4-aminophenyl)-5-aminobenzimidazole is:

.

A polyimide copper-clad laminate. The polyimide copper-clad laminate includes a copper foil and a polyimide film bonded to the surface of the copper foil. The polyimide film is composed of the polyimide film as described above. The amine composition is formed by coating the surface of the copper foil and then baking to remove the solvent.

的側鏈基團且所述聚醯亞胺膜為非對稱結構，能夠破壞聚醯亞胺主鏈的穩定性，從而阻止聚醯亞胺膜的分子間及分子內電荷轉移CTC作用的生成，抑制聚醯亞胺膜在可見光區的強烈吸收，從而使得聚醯亞胺膜透明。 The polyimide film, the polyimide film and the polyimide copper-clad laminate provided by the invention have polar groups including nitrogen heterocycles, ether groups and other polar groups, and the molecular structural formula is:

The side chain groups and the polyimide film have an asymmetric structure, which can destroy the stability of the polyimide main chain, thereby preventing the generation of intermolecular and intramolecular charge transfer CTC of the polyimide film, Suppresses the strong absorption of the polyimide film in the visible light region, thereby making the polyimide film transparent.

100:Polyimide copper clad laminate

10:Polyimide membrane

20:Copper foil

Figure 1 is a schematic cross-sectional view of a copper-clad laminate according to a preferred embodiment of the present invention.

Please refer to FIG. 1 . A preferred embodiment of the present invention provides a polyimide composition, which is mainly used to make the polyimide film 10 bonded to the surface of the copper foil 20 in the polyimide copper-clad laminate 100 .

The polyimide composition is mainly polymerized by dianhydride monomer and diamine monomer.

；所述二胺單體為非對稱結構且具有第二極性基團，其中，所述第二極性基團為氮雜環、醚基-中的一種或兩種。 Wherein, the dianhydride monomer has an asymmetric structure, and the dianhydride monomer has a first polar group and a side chain group, wherein the first polar group is an ester group, and the side chain group The molecular structure formula of

; The diamine monomer has an asymmetric structure and has a second polar group, wherein the second polar group is one or both of a nitrogen heterocycle and an ether group.

。 In this embodiment, the dianhydride is cyclododecane-1,1-diylbis(2-methyl-4,1-phenylene)bis(1,3-dioxo-1,3 -ethyl dihydroisobenzofuran-5-carboxylate), the cyclododecane-1,1-diylbis(2-methyl-4,1-phenylene)bis(1,3- Ethyl dioxo-1,3-dihydroisobenzofuran-5-carboxylate is abbreviated as TBIS-DMPN. The molecular structural formula of TBIS-DMPN is:

.

，所述4,4'-二氨基-2,2'-聯吡啶的分子結構式是：

，所述2,6-二氨基吡啶的分子結構式是：

，所述2-(4-氨基苯基)-5-氨基苯並咪唑的分子結構式是：

。 In other embodiments, the dianhydride may also be other dianhydrides having the first polar group and the side chain group. Wherein, the diamine monomer is a diamine monomer having a nitrogen heterocycle. In this embodiment, the diamine monomer is 3,5-diamino-1,2,4-triazole, 4,4'-diamino-2,2'-bipyridine, 2,6- At least one of diaminopyridine and 2-(4-aminophenyl)-5-aminobenzimidazole. Among them, the 3,5-diamino-1,2,4-triazole is abbreviated as DTZ and its molecular structural formula is:

, the molecular structural formula of the 4,4'-diamino-2,2'-bipyridine is:

, the molecular structural formula of the 2,6-diaminopyridine is:

, the molecular structural formula of the 2-(4-aminophenyl)-5-aminobenzimidazole is:

.

。 Wherein, the diamine monomer may also be a diamine monomer having an ether group and an asymmetric structure. In this embodiment, the diamine monomer is 1,3-bis(3-aminophenoxy)benzene, abbreviated as APB-N. The 1,3-bis(3-aminophenoxy)benzene is The molecular structural formula is:

.

。 In other embodiments, the diamine monomer with an ether group and an asymmetric structure can also be 1,3-bis(3-aminophenoxy)benzene, referred to as TPE-R. The molecular structure of the TPE-R The formula is:

.

。 In other embodiments, the diamine monomer with an ether group and an asymmetric structure can also be 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3, 3,3-Hexafluoropropane, abbreviation: HFBAPP, the molecular structural formula of HFBAPP is:

.

，所述2,2-雙[4-(4- 氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷，簡稱：HFBAPP，所述HFBAPP的分子結構式是：

。 Wherein, the diamine monomer may also be a diamine monomer having _-CF3 and an asymmetric structure. Specifically, the diamine monomer is 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether, 2,2-bis[4-(4-aminophenoxy) Phenyl]-1,1,1,3,3,3-hexafluoropropane and 2,2'-bis(trifluoromethyl)diaminobiphenyl, the 2,2'-bis(trifluoromethyl) )-4,4'-diaminophenyl ether is referred to as 6FODA, and the 2,2'-bis(trifluoromethyl)diaminobiphenyl is referred to as TFMB. The molecular structural formula of 6FODA is:

, the 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, abbreviation: HFBAPP, the molecular structural formula of the HFBAPP yes:

.

。 The molecular structural formula of TFMB is:

.

。 Wherein, the diamine monomer may also be a diamine monomer having -SO ₂ - and an asymmetric structure. Specifically, the diamine monomer is 4,4'-diaminodiphenyl sulfone, abbreviated as 4,4'DDS. The molecular structural formula of the 4,4'DDS is:

.

Wherein, the molar ratio of the dianhydride monomer to the diamine monomer is: 0.8-1.2.

In this embodiment, in the polyimide composition, the dianhydride monomer is 0.08-0.12 mol, and the diamine monomer is 0.08-0.12 mol.

Wherein, the polyimide composition also contains a solvent, and in the polyimide composition, the weight percentage of the solvent is 70%-85%. Wherein, the solvent is preferably a bipolar aprotic solvent. The bipolar aprotic solvent may be dimethylformamide (DMF), dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), etc. The added amount of the solvent can be changed as needed, as long as the diamine monomer and the dianhydride monomer can be completely dissolved.

The preparation method of the polyimide composition can be: adding diamine monomer and dianhydride monomer into a 500ml reaction bottle (the molar ratio of the diamine monomer to the dianhydride monomer is 1:1 ), solvent GBL/NMP (the weight ratio of GBL/NMP is 1:1), the solid content in the reaction bottle is divided into 20%-25%, stir Stirring for 12 hours, heating to 80°C and stirring for 4 hours means that a reaction occurs. During the reaction, add xylene (the weight of xylene is 1/5 of the weight of the solvent GBL/NMP), then raise the temperature to 180°C and set up a reflux pipe. (xylene is added to the reflux tube), and the reaction is carried out for 16-18 hours to obtain a transparent polyimide composition solution.

Please refer to FIG. 1 , which shows a polyimide copper-clad laminate 100 used to make a circuit board (not shown). The polyimide copper-clad laminate 100 includes a copper foil 20 and a polyimide film 10 bonded to a surface of the copper foil 20 . The surface of the copper foil 20 has low roughness. The polyimide film 10 is formed by coating the polyimide composition on the surface of the copper foil 20 and then baking to remove the solvent in a nitrogen atmosphere.

In this embodiment, the copper foil 20 is an electrolytic copper foil, the thickness of the copper foil 20 is 12 microns, and the thickness of the polyimide film is 12 to 25 microns; the baking temperature is 200 ℃-250℃.

In this embodiment, the polyimide copper-clad substrate 100 includes the copper foil 20 , and the polyimide film 10 is located on the copper foil 20 .

Because the polyimide composition is composed of the above-mentioned dianhydride monomer and diamine monomer, the solid state of the obtained polyimide composition has an asymmetric structure and has a first polar group, a third polar group, and a first polar group. Dipolar groups and side chain groups can destroy the stability of the polyimide main chain, thereby preventing the generation of intermolecular and intramolecular charge transfer CTC of the polyimide film, and inhibiting the polyimide film from visible light. The strong absorption in the area makes the polyimide film transparent.

Wherein, the copper foil 20 of the polyimide copper-clad laminate 100 and the polyimide film 10 are directly combined, and no glue is provided between the copper foil 20 and the polyimide film 10 The adhesive layer can further improve the transmittance of the polyimide film 10 and save costs.

A method for making the above-mentioned polyimide copper-clad laminate 100:

First, a copper foil 20 is provided, and the thickness of the copper foil 20 is 12 microns.

Next, a polyimide composition is provided, and the polyimide composition is coated on the surface of the copper foil 20 .

Again, the solvent is removed by baking, so that the polyimide composition on the surface of the copper foil 20 is baked to remove the solvent, and the polyimide film 10 bonded to the surface of the copper foil 20 is obtained, that is, the copper-clad laminate 100 is obtained.

The present invention also provides a polyimide film 10. The polyimide film 10 is formed by coating the polyimide composition on the surface of a substrate and then baking to remove the solvent.

Wherein, the base material can be a release film, metal foil, resin and other base materials commonly used in preparing polyimide films. The solvent polyimide is removed by baking, thereby obtaining a polyimide film 10 bonded to the surface of the substrate.

The polyimide composition of the present invention will be further described below through specific examples. Among them, the abbreviations involved in Comparative Examples 1-17 and their corresponding Chinese names and molecular structural formulas are as follows:

。 The Chinese name of ODA is: 4,4'-diaminodiphenyl ether, and its molecular structural formula is:

.

。 The Chinese name of TPE-R is: 1,3-bis(4'-aminophenoxy)benzene, and its molecular structural formula is:

.

。 The Chinese name of NBDA is: bicyclo[2.2.1]heptanedimethylamine, and its molecular structural formula is:

.

。 The Chinese name of 44'DDS is: 4,4'-diaminodiphenylene sulfide, and its molecular structural formula is:

.

。 The Chinese name of 6FODA is: 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether, and its molecular structural formula is:

.

。 The Chinese name of BFAF is: 9,9-bis(4-amino-3-fluorophenyl)fluorene, and its molecular structural formula is:

.

。 The Chinese name of TFMB is: 2,2'-bis(trifluoromethyl)diaminobiphenyl, and its molecular structural formula is:

.

。 The Chinese name of HFBAPP is: 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, and its molecular structural formula is:

.

。 The Chinese name of TAHO is: p-phenyl di(trimellitic acid ester) dianhydride, and its molecular structural formula is:

.

。 The Chinese name of HPMDA is: hydrogenated pyromellitic dianhydride, and its molecular structural formula is:

.

。 The Chinese name of PMDA is: pyromellitic dianhydride, and its molecular structural formula is:

.

。 6FDA’s Chinese name is: hexafluorodianhydride, molecular structure formula:

.

Example 1

Add DTZ (0.1mol, 9.91g) and the solvent GBL/NMP (1:1, 248.36g) into a 500mL reaction bottle respectively. Stir at high speed until dissolved, then add TBIS-DMPN (0.1mol, 72.88g). Type 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours. During the reaction, add xylene (49.67g), then heat to 180°C and set up a reflux pipe (add in the reflux pipe (xylene), react at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition solution.

Example 2

Add 4,4'-diamino-2,2'-bipyridine (0.1mol, 18.62g) and solvent GBL/NMP (1:1, 274.5g) into a 500mL reaction bottle respectively, and stir at high speed until dissolved. Then add TBIS-DMPN (0.1mol, 72.88g), solid content 20-25%, stir for 12 hours, heat to 80℃, stir and dissolve for 4 hours, during the reaction, add xylene (54.9g), then heat to 180℃ and set up a reflux pipe (Xylene is added to the reflux tube), react at a constant temperature of 180°C for 16-18 hours, and a transparent polyimide composition solution can be prepared.

Example 3

Add APB-N (0.1 mol, 29.23g) and solvent GBL/NMP (1:1, 306.34g) into a 500mL reaction bottle respectively, stir at high speed until dissolved, then add TBIS-DMPN (0.1mol, 72.88g) , solid content 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours, add xylene (61.27g) during the reaction, then heat to 180°C and set up a reflux pipe (reflux pipe Add xylene), react at a constant temperature of 180°C for 16-18 hours, and a transparent polyimide composition solution can be prepared.

Comparative example 1

Add DTZ (0.1mol, 9.91g) and solvent GBL/NMP (1:1, 167.23g) into a 500mL reaction bottle respectively, stir at high speed until dissolved, then add TAHQ (0.1mol, 45.83g), and separate the solid 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours. During the reaction, add xylene (33.44g), then heat to 180°C and set up a reflux pipe (the reflux pipe is added with dimethylbenzene) Toluene), react at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition solution.

Comparative example 2

Add 4,4'-diamino-2,2'-bipyridine (0.1mol, 18.62g) and solvent GBL/NMP (1:1, 193.37g) into a 500mL reaction bottle respectively, and stir at high speed until dissolved. Then add TAHQ (0.1mol, 45.83g), the solid content is 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours, during the reaction, add xylene (38.67g), and then raise the temperature to 180°C and set up a reflux pipe (xylene is added to the reflux pipe), and react at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition solution.

Comparative example 3

Add APB-N (0.1 mol, 29.23g) and solvent GBL/NMP (1:1, 225.2g) to a 500 mL reaction bottle respectively. Stir at high speed until dissolved, then add TAHQ (0.1 mol, 45.83g). Type score 20-25%, Stir for 12 hours and heat to 80°C. Stir and dissolve for 4 hours. During the reaction, add 45.04g of xylene), then raise the temperature to 180°C and set up a reflux pipe (xylene is added to the reflux pipe) at 180°C. After reacting for 16-18 hours at a constant temperature, a transparent polyimide composition solution can be prepared.

Comparative example 4

Add DTZ (0.1mol, 9.91g) and solvent GBL/NMP (1:1, 163.00g) into a 500mL reaction bottle respectively, stir at high speed until dissolved, then add 6FDA (0.1mol, 44.42g), and separate the solid 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours. During the reaction, add xylene (32.60g), then heat to 180°C and set up a reflux pipe (the reflux pipe is added with dimethylbenzene) Toluene), react at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition solution.

Comparative example 5

Add 4,4'-diamino-2,2'-bipyridine (0.1mol, 18.62g) and solvent GBL/NMP (1:1, 189.14g) into a 500mL reaction bottle respectively, and stir at high speed until dissolved. Then add 6FDA (0.1mol, 44.42g), the solid content is 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours, during the reaction, add xylene (37.82g), and then raise the temperature to 180°C and set up a reflux pipe (xylene is added to the reflux pipe), and react at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition solution.

Comparative example 6

Add APB-N (0.1 mol, 29.23g) and solvent GBL/NMP (1:1, 220.97g) respectively into a 500mL reaction bottle. After stirring at high speed until dissolved, add 6FDA (0.1mol, 44.42g). Type 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours. During the reaction, add xylene (44.19g), then heat to 180°C and set up a reflux pipe (add in the reflux pipe (xylene), react at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition solution.

Comparative example 7

Add DTZ (0.1mol, 9.91g) and solvent GBL/NMP (1:1, 96.98g) into a 500mL reaction bottle respectively, stir at high speed until dissolved, then add HPMDA (0.1mol, 22.42g), and separate the solid 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours, during the reaction, add two Toluene (19.39g), then raise the temperature to 180°C and set up a reflux pipe (xylene is added to the reflux pipe), and react at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition solution.

Comparative example 8

Add 4,4'-diamino-2,2'-bipyridine (0.1mol, 18.62g) and solvent GBL/NMP (1:1, 123.12g) into a 500mL reaction bottle respectively, and stir at high speed until dissolved. Then add HPMDA (0.1mol, 22.42g) with a solid content of 20-25%. Stir for 12 hours. After heating to 80°C, stir and dissolve for 4 hours. During the reaction, add xylene (24.62g) and raise the temperature again. to 180°C and set up a reflux pipe (xylene is added to the reflux pipe), and react at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition solution.

Comparative example 9

Add APB-N (0.1 mol, 29.23g) and solvent GBL/NMP (1:1, 154.95g) to a 500mL reaction bottle respectively. Stir at high speed until dissolved, then add HPMDA (0.1mol, 22.42g). Type 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours. During the reaction, add xylene (30.99g), then heat to 180°C and set up a reflux pipe (add in the reflux pipe (xylene), react at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition solution.

Comparative example 10

Add ODA (0.1 mol, 20.02g) and solvent GBL/NMP (1:1, 278.71g) to a 500mL reaction bottle respectively. Stir at high speed until dissolved, then add TBIS-DMPN (0.1mol, 72.88g). Type 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours. During the reaction, add xylene (55.74g), then heat to 180°C and set up a reflux pipe (add in the reflux pipe (xylene), react at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition solution.

Comparative example 11

Add TPE-R (0.1mol, 29.23g) and solvent GBL/NMP (1:1, 306.33g) into a 500mL reaction bottle respectively, stir at high speed until dissolved, then add TBIS-DMPN (0.1mol, 72.88g) , the solid content is 20-25%, stir for 12 hours, heat to 80℃, stir and dissolve for 4 hours, during the reaction, Add xylene (61.27g), then raise the temperature to 180°C and set up a reflux pipe (xylene is added to the reflux pipe). React at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition. solution.

Comparative example 12

Add NBDA (0.1 mol, 15.43g) and solvent GBL/NMP (1:1, 264.91g) respectively into a 500mL reaction bottle. After stirring at high speed until dissolved, add TBIS-DMPN (0.1mol, 72.88g). Type 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours. During the reaction, add xylene (52.98g), then heat to 180°C and set up a reflux pipe (add in the reflux pipe (xylene), react at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition solution.

Comparative example 13

Add 44'DDS (0.1mol, 24.83g) and solvent GBL/NMP (1:1, 293.12g) into the 500mL reaction bottle respectively, stir at high speed until dissolved, then add TBIS-DMPN (0.1mol, 72.88g) , solid content is 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours, add xylene (58.62g) during the reaction, then heat to 180°C and set up a reflux pipe (reflux pipe Add xylene), react at a constant temperature of 180°C for 16-18 hours, and a transparent polyimide composition solution can be prepared.

Comparative example 14

Add 6FODA (0.1mol, 33.62g) and solvent GBL/NMP (1:1, 319.50g) to a 500mL reaction bottle respectively. Stir at high speed until dissolved, then add TBIS-DMPN (0.1mol, 72.88g). Type 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours. During the reaction, add xylene (63.90g), then heat to 180°C and set up a reflux pipe (add in the reflux pipe (xylene), react at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition solution.

Comparative example 15

Add TFMB (0.1mol, 32.02g) and solvent GBL/NMP (1:1, 314.70g) to a 500mL reaction bottle respectively. Stir at high speed until dissolved, then add TBIS-DMPN (0.1mol, 72.88g). Type 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours. During the reaction, add xylene (62.94g), then heat to 180°C and set up a reflux pipe (add in the reflux pipe (xylene), react at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition solution.

Comparative example 16

Add BFAF (0.1 mol, 38.44g) and solvent GBL/NMP (1:1, 333.96g) into a 500mL reaction bottle respectively. Stir at high speed until dissolved, then add TBIS-DMPN (0.1mol, 72.88g). Type 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours. During the reaction, add xylene (66.79g), then heat to 180°C and set up a reflux pipe (add in the reflux pipe (xylene), react at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition solution.

Comparative example 17

Add HFBAPP (0.1 mol, 38.44g) and solvent GBL/NMP (1:1, 333.96g) to a 500mL reaction bottle respectively. Stir at high speed until dissolved, then add TBIS-DMPN (0.1mol, 72.88g). Type 20-25%, stir for 12 hours, heat to 80°C, stir and dissolve for 4 hours. During the reaction, add xylene (66.79g), then heat to 180°C and set up a reflux pipe (add in the reflux pipe With xylene), react at a constant temperature of 180°C for 16-18 hours to prepare a transparent polyimide composition solution.

The polyimide compositions prepared in the above-mentioned Examples 1 to 3 and Comparative Examples 1 to 17 were respectively coated on the surface of the copper foil 20, and the copper foil 20 coated with the polyimide composition was placed at high temperature. Under the environment, the polyimide composition is baked to remove the solvent to form the polyimide film 10 bonded to the surface of the copper foil 20 to obtain the polyimide copper-clad laminate 100 .

The copper clad laminate 100 was subjected to a penetration test, a copper peeling strength test and a tin drift test respectively. See Table 1 and Table 2 for test results. Among them, in the tin bleaching test, if the tin bleaching test lasts for 30 seconds at a temperature of 288°C and the PI film does not discolor or bubble, the tin bleaching test result is "passed", indicating that the polyimide copper-clad laminate 100 has reached Requirements for solder float testing.

As can be seen from the above table, the polyimides of Examples 1 to 3 are composed of dianhydride monomers (TBIS-DMPN) with bulky side chain groups, combined with polar groups (nitrogen heterocycles, ether groups) and are asymmetric The structural diamine monomer reduces the degree of charge transfer between molecules and intramolecules, the transmittance is >88% (550nm), and the generated polyimide film and copper foil have good peel strength (>0.8Kgf/ cm) and heat resistance (288℃/30s, PASS)

From Examples 1 to 3 and Comparative Examples 10-16, TBIS-DMPN (diacid anhydride monomer) is combined with different diamine monomers. The diamine monomer used in Comparative Examples 10-16 has a polar group (-CF ₃ , -O-, -SO ₂ -), no benzene ring or bulky side chain group (-CF ₃ , benzene ring), their transmittance is less than 88% (550nm), while Comparative Example 14 and Comparative Example 17, which contains a diamine monomer with a polar group (-O-) and a bulky side chain group (-CF ₃ ), has a transmittance close to or greater than 88% (550nm), but because The peeling strength between the fluorine-containing monomer and the copper foil substrate is insufficient (<0.8Kgf/cm), and Comparative Examples 4 to 6 use 6FDA (diacid anhydride) with the same diamine monomer as Examples 1 to 3, because 6FDA is a monomer containing fluorine groups, and the glass strength of the polyimide film and copper foil substrate produced accordingly is insufficient; among them, the diamine monomer APB-N (Example 3) and ODA (Comparative Example 9) and TPE -R (Comparative Example 10) both have polarity (-O-), while APB-N has one more -O- group than ODA, and the other is APB-N (meta position) compared to TPE-R (para position). ), is an asymmetric structure. Compared with the meta-element structure, it has a better effect of hindering the arrangement of molecules. It can simultaneously reduce the charge transfer within and between molecules, and the light transmittance is better.

Comparative Examples 1-3 use TAHQ with the same diamine monomer as Examples 1-3. TAHQ and TBIS-DMPN have the same ester group, which can reduce intramolecular charge transfer, but has no side chain bulky groups. The molecule It is easy to arrange between molecules, causing charge transfer between molecules, thereby making the transparency less than 88% (550nm).

Comparative Examples 7-9 use HPMDA (1,2,4,5-cyclohexanetetracarboxylic dianhydride) with the same diamine monomer as in Examples 1-3. HPMDA is a benzene ring-free monomer (TBIS-DMPN It also has side chain groups without benzene rings), which reduces the degree of intramolecular charge transfer. However, because it has no side chain groups, it cannot prevent the generation of intermolecular charge transfer complexes. The transparency is less than 88% (550nm), and HPMDA It is aliphatic and has obviously insufficient heat resistance (288℃/30s, NG).

Therefore, the transparent polyimide composition of the present invention is polymerized from a dianhydride monomer and a diamine monomer. The above-mentioned dianhydride monomer is TBIS-DMPN, and the above-mentioned diamine monomer has a nitrogen-containing heterocyclic ring. , ether groups and other polar groups and a diamine monomer with an asymmetric structure, so that the transparent polyimide film of the present invention maintains good adhesion and heat resistance to the copper foil and maintains transparency >88% ( 550nm).

的側鏈基團且所述聚醯亞胺膜為非對稱結構，能夠破壞聚醯亞胺主鏈的穩定性，從而阻止聚醯亞胺膜的分子間及分子內電荷轉移CTC作用的生成，抑制聚醯亞胺膜在可見光區的強烈吸收，從而使得聚醯亞胺膜透明。 The polyimide film, the polyimide film and the polyimide copper-clad laminate provided by the invention have polar groups including nitrogen heterocycles, ester groups, ether groups and other polar groups, and the molecular structural formula is: :

The side chain groups and the polyimide film have an asymmetric structure, which can destroy the stability of the polyimide main chain, thereby preventing the generation of intermolecular and intramolecular charge transfer CTC of the polyimide film, Suppresses the strong absorption of the polyimide film in the visible light region, thereby making the polyimide film transparent.

The above are only preferred embodiments of the present invention, and are not intended to limit the present invention in any form. Although the preferred embodiments of the present invention have been disclosed above, they are not intended to limit the present invention. Any person familiar with the art may , without departing from the scope of the technical solution of the present invention, the technical content disclosed above can be used to make some changes or modifications to equivalent implementations with equivalent changes. However, without departing from the technical solution content of the present invention, according to the technical essence of the present invention, Any simple modifications, equivalent changes and modifications made to the above embodiments still fall within the scope of the technical solution of the present invention.

100:Polyimide copper clad laminate

10:Polyimide membrane

20:Copper foil

Claims (5)

A polyimide film with a light transmittance greater than 88% is produced by coating and baking a polyimide composition. The polyimide composition is polymerized by a dianhydride monomer and a diamine monomer, wherein , the dianhydride monomer has a molecular structural formula of

Cyclodecane-1,1-diylbis(2-methyl-4,1-phenylene)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5- Ethyl carboxylate), wherein the diamine monomer is 3,5-diamino-1,2,4-triazole, 4,4'-diamino-2,2'-bipyridine, 2, At least one of 6-diaminopyridine and 2-(4-aminophenyl)-5-aminobenzimidazole; wherein, the molecular structure of the 3,5-diamino-1,2,4-triazole The formula is:

, the molecular structural formula of the 4,4'-diamino-2,2'-bipyridine is:

, the molecular structural formula of the 2,6-diaminopyridine is:

, the molecular structural formula of the 2-(4-aminophenyl)-5-aminobenzimidazole is:

. The polyimide film with a transmittance greater than 88% as described in claim 1, wherein the molar ratio of the dianhydride monomer to the diamine monomer is: 0.8-1.2. The polyimide film with a transmittance greater than 88% as described in claim 2, wherein the polyimide composition also contains a solvent, and in the polyimide composition, the solvent The weight percentage is 70%-85%. The polyimide film with a light transmittance greater than 88% as described in claim 3, wherein the solvent is dimethyl formamide, dimethyl acetamide, N-methylpyrrolidone, dimethyl styrene at least one of them. A polyimide copper-clad laminate, wherein the polyimide copper-clad laminate includes copper foil and a polyimide film with a transmittance greater than 88% as described in any one of claims 1-4, and the polyimide copper-clad laminate The imine film is bonded to the surface of the copper foil.

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