TW201508040A - Polyimide adhesive - Google Patents

Abstract

The present invention relates to an adhesive of polyimide comprising products in copolymerization of reactants selected from following monomers of tetracarboxylic dianhydride and aromatic diamine: (a) triazole diamine; (b) pyromellitic dianhydride; and (c) oxy-dianiline, wherein weight ratio of tetracarboxylic dianhydride and aromatic diamine is 1:0.7-1.3, and the amount of triazole diamine is less 70% based on total weight of amine groups.

Description

Polyimine adhesive

The present invention relates to a polyimide conjugate adhesive suitable for use in a copper foil substrate, and more particularly to a polyimide conjugate adhesive for use in a copper foil substrate having high heat resistance, high adhesion, and high flatness.

Soft printed circuit boards have the advantages of softness, lightness, thinness and flexibility. They are widely used in notebook computers, digital related devices, mobile phones, and LCDs in the trend of fast, thin, short, and small trends in telecom electronic products. The display waits for the purpose.

The traditional soft board material is mainly composed of a three-layer structure of polyimine (PI) film/adhesive/copper foil, and the adhesive is mainly epoxy resin/acrylate, but the heat resistance of the adhesive is The dimensional stability is not good, and the long-term use temperature is limited to 100-200 ° C, which makes the application area of the three-layered flexible board substrate limited. The newly developed two-layer non-adhesive soft board substrate (2-Layer FCCL) consists only of PI film/copper foil, because it does not require the use of an adhesive agent to increase the reliability and application range of the product for long-term use.

At present, most of the two-layer flexible printed circuit substrates are coated with a polyimide precursor, polyacrylamide (PAA), coated on a copper foil, dried, and then cured to obtain a poly bond directly bonded to the copper foil.醯 imine film. Usually, polylysine is synthesized by reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine. However, since the general copper foil of the polyimine has poor bondability, it is necessary to select a monomer-modified polyimine having high copper foil bondability.

In addition, in the development of a polyimide-free copper foil laminate material without an adhesive type, in addition to improving the copper foil bondability of polyimine, there is a problem that the polyimide/copper foil after bonding is curled. .

It is an object of the present invention to provide a polyimide pigment adhesive for use in a copper foil substrate which has high heat resistance, high adhesion and high flatness.

In order to achieve the above object, the present invention is a polyimine adhesive which is obtained by copolymerizing a reactant comprising the following monomers selected from the group consisting of tetracarboxylic dianhydride and aromatic diamine: (a) trinitrogen a heterobenzene diamine; (b) pyromellitic dianhydride (PMDA); and (c) a diaminodiphenyl ether (ODA), wherein the weight ratio of the tetracarboxylic dianhydride to the aromatic diamine is 1:0.7-1.3, and the content of the triazabenzenediamine is less than 70% of the amine group. A triazabenzene diamine suitable for use in the preparation of the polyimine adhesive of the present invention is, for example, 3,5-diamino-1,2,4-triazabenzene (DATA).

The Cu-N bond is formed with the metal copper by the nitrogen atom on the triazabenzene diamine functional group to achieve a bonding strength with the copper metal. Further, the main chain structure of the pyromellitic dianhydride exhibits high rigidity, and the problem of curling of the polyimide/copper foil after bonding can be improved. In addition, since the reactivity of the DATA monomer is not ideal, the addition of ODA can be carried out to compensate for the lack of viscosity, thereby achieving the film formation requirement.

In addition, the inventors have found through long-term studies that the composition of the polyimine imide adhesive used in the preparation of the present invention does not contain a nitrogen atom and a metal copper on the functional group if the triazine benzene diamine monomer is not contained. The Cu-N bond is formed, and the bondability with the copper foil is lowered. However, if the content of the arsenazo diamine monomer is too high, for example, 70% by weight or more of the amine group composition, the thermal expansion coefficient of the obtained polyimine is too large compared with the thermal expansion coefficient of the copper foil, and the polyimine after bonding / Copper foil will cause curling. Therefore, the content of the triazabenzene diamine monomer must be within a specific range in order to achieve both the adhesion to the copper foil and the occurrence of curling.

In one aspect of the invention, the tetracarboxylic dianhydride further comprises a biphenyltetracarboxylic dianhydride, wherein the molar ratio of the biphenyltetracarboxylic dianhydride to the pyromellitic dianhydride is 1:0.2- 5. In another aspect, the tetracarboxylic dianhydride further comprises benzophenone tetracarboxylic dianhydride, wherein the molar ratio of benzophenone tetracarboxylic dianhydride to pyromellitic dianhydride is 1:0.2-5.

In one aspect of the invention, the aromatic diamine further comprises 4,4'-diaminobenzophenone, wherein the molar ratio of the triazabenzene diamine to the 4,4'-diaminobenzophenone It is 1:0.2-5. In another aspect, the aromatic diamine further comprises 4,4'-diaminodiphenyl ether, wherein the molar ratio of the triazabenzene diamine to the 4,4'-diaminodiphenyl ether is 1 : 0.2-5.

Compared with the prior art, the polyimine adhesive of the present invention has the advantages of good appearance, high heat resistance, high adhesion, high flatness and good light transmittance.

The present invention is further described below in conjunction with specific embodiments:

The present invention is a polyamidene adhesive which is obtained by copolymerizing a reactant comprising the following monomers selected from the group consisting of tetracarboxylic dianhydride and aromatic diamine: (a) triazabenzene diamine; (b) pyromellitic dianhydride (PMDA); and (c) diaminodiphenyl ether (ODA), wherein the weight ratio of the tetracarboxylic dianhydride to the aromatic diamine is 1:0.7-1.3, And the content of the arsenazo diamine is less than 70% of the amine group. A triazabenzene diamine suitable for use in the preparation of the polyimine adhesive of the present invention is, for example, 3,5-diamino-1,2,4-triazabenzene (DATA).

Triazabenzene diamine suitable for use in preparing the polyimine adhesive of the present invention, for example, 2,4-bis(4-aminoanilino)-6-anilino-1,3,5-triaza Benzene, 2,4-bis(3-aminoanilino)-6-anilino-1,3,5-triazabenzene, 2,4-bis(4-aminoanilino)-6-benzene Amino-1,3,5-triazabenzene, 2,4-bis(3-aminoanilino)-6--benzylamino-1,3,5-triazabenzene, 2,4 - bis(4-aminoanilino)-6-naphthylamino-1,3,5-triazabenzene, 2,4-bis(4-aminoanilino)-6-benzidine-1, 3,5-triazabenzene, 2,4-bis(4-aminoanilino)-6-benzidine-1,3,5-triazabenzene, 2,4-bis(3-amino group Anilino)-6-benzidine-1,3,5-triazabenzene, 2,4-bis(4-aminoanilino)-6-diphenylmethylamino-1,3,5-tri Azabenzene, 2,4-bis(4-aminoanilino)-6-dinaphthylamino-1,3,5-triazabenzene, 2,4-bis(4-aminoanilino)- 6-N-toluidine-1,3,5-triazabenzene, 2,4-bis(4-aminoanilino)-6-N-naphthylamino-1,3,5-triazo Heterobenzene, 2,4-bis(4-aminoanilino)-6-methylamino-1,3,5-triazabenzene, 2,4-bis(3-aminoanilino)-6- Methylamino-1,3,5-triazabenzene, 2,4-bis(4-aminoanilino)-6-ethylamino-1,3,5 -Triazabenzene, 2,4-bis(3-aminoanilino)-6-ethylamino-1,3,5-triazabenzene, 2,4-bis(4-aminoanilino) -6-dimethylamino-1,3,5-triazabenzene, 2,4-bis(3-aminoanilino)-6-dimethylamino-1,3,5-triazabenzene , 2,4-bis(4-aminoanilino)-6-diethylamino-1,3,5-triazabenzene, 2,4-bis(4-aminoanilino)-6-di Butyryl-1,3,5-triazabenzene, 2,4-bis(4-aminoanilino)-6-amino-1,3,5-triazabenzene, 2,4-double (3-aminoanilino)-6-amino-1,3,5-triazabenzene; and 3,5-diamino-1,2,4-triazabenzene, etc., of which 3 is preferred , 5 diamino-1,2,4-triazabenzene.

(Example 1)

Add 200 ml of the solvent dimethylacetamide (DMAC) to a 500 ml reactor equipped with water jacket, stir evenly at 200 r/min, and slowly add 3,5-diamino-1,2,4-three. 7.50 g of azabenzene (DATA), 3.90 g of diaminodiphenyl ether (ODA) and 6.80 g of 4,4'-diaminobenzophenone were added to the reactor at a temperature of 20 ° C and stirred for 2 hours. 15.11 g of biphenyltetracarboxylic dianhydride (BPDA) and 16.55 g of pyromellitic dianhydride (PMDA) were slowly added, and the stirring speed was adjusted to 300 r/min to continue stirring, and the reaction was stopped after 3 hours.

The polylysine solution obtained above was coated on a copper foil manufactured by Nippon Mining Co., Ltd., model: BHY22BT, thickness 18um, and then baked at 160 ° C for 10 minutes, and sequentially under the protection of nitrogen at 120 ° C, 160 After heating at °C, 200 ° C, 250 ° C, 300 ° C and 380 ° C for 20 minutes, the poly-proline can be amidated to form a polyimide film, and the film thickness is 25 μm to obtain a non-adhesive soft copper foil substrate.

(Example 2)

Add 200 ml of the solvent dimethylacetamide (DMAC) to a 500 ml reactor equipped with water jacket, stir evenly at 200 r/min, and slowly add 3,5-diamino-1,2,4-three. 7.50 g of azabenzene (DATA), 3.90 g of diaminodiphenyl ether (ODA) and 6.80 g of 4,4'-diaminobenzophenone were added to the reactor at a temperature of 20 ° C and stirred for 2 hours. 24.18 g of biphenyltetracarboxylic dianhydride (BPDA) and 6.58 g of pyromellitic dianhydride (PMDA) were slowly added, and the stirring speed was adjusted to 300 r/min to continue stirring, and the reaction was stopped after 3 hours.

The polylysine solution obtained above was coated on a copper foil manufactured by Nippon Mining Co., Ltd., model: BHY22BT, thickness 18um, and then baked at 160 ° C for 10 minutes, and sequentially under the protection of nitrogen at 120 ° C, 160 After heating at °C, 200 ° C, 250 ° C, 300 ° C and 380 ° C for 20 minutes, the poly-proline can be amidated to form a polyimide film, and the film thickness is 25 μm to obtain a non-adhesive soft copper foil substrate.

(Example 3)

Add 200 ml of the solvent dimethylacetamide (DMAC) to a 500 ml reactor equipped with water jacket, stir evenly at 200 r/min, and slowly add 3,5-diamino-1,2,4-three. 7.50 g of azabenzene (DATA), 3.90 g of diaminodiphenyl ether (ODA) and 6.80 g of 4,4'-diaminobenzophenone were added to the reactor, the temperature was kept at 20 ° C, stirred for 2 hours, then 18.00 g of benzophenonetetracarboxylic dianhydride (BTDA) and 6.58 g of pyromellitic dianhydride (PMDA) were slowly added, and the stirring speed was adjusted to 300 r/min to continue stirring, and the reaction was stopped after 3 hours.

The polylysine solution obtained above was coated on a copper foil manufactured by Nippon Mining Co., Ltd., model: BHY22BT, thickness 18um, and then baked at 160 ° C for 10 minutes, and sequentially under the protection of nitrogen at 120 ° C, 160 After heating at °C, 200 ° C, 250 ° C, 300 ° C and 380 ° C for 20 minutes, the poly-proline can be amidated to form a polyimide film, and the film thickness is 25 μm to obtain a non-adhesive soft copper foil substrate.

(Example 4)

Add 200 ml of the solvent dimethylacetamide (DMAC) to a 500 ml reactor equipped with water jacket, stir at 200 r/min, and slowly add 3,5-diamino-1,2,4-three. Azabenzene (DATA) 4.65g, diaminodiphenyl ether (ODA) 2.15g and 4,4'-diaminobenzophenone 21.62g were added to the reactor, the temperature was kept at 20 ° C, stirred for 2h, then slowly 18.04 g of benzophenonetetracarboxylic dianhydride (BTDA) and 6.66 g of pyromellitic dianhydride (PMDA) were added, and the stirring speed was adjusted to 300 r/min to continue stirring, and the reaction was stopped after 3 hours.

The polylysine solution obtained above was coated on a copper foil manufactured by Nippon Mining Co., Ltd., model: BHY22BT, thickness 18um, and then baked at 160 ° C for 10 minutes, and sequentially under the protection of nitrogen at 120 ° C, 160 After heating at °C, 200 °C, 250 °C, 300 °C and 380 °C for 20 min, the polylysine can be amidated to form a polyimide film, and the film thickness is 25 μm, and a non-adhesive soft copper foil substrate is obtained.

(Example 5)

Add 200 ml of the solvent dimethylacetamide (DMAC) to a 500 ml reactor equipped with water jacket, stir evenly at 200 r/min, and slowly add 3,5-diamino-1,2,4-three. Azabenzene (DATA) 10.35g and diaminodiphenyl ether (ODA) 2.15g were added to the reactor, the temperature was kept at 20 ° C, stirred for 2 hours, then slowly added biphenyltetracarboxylic dianhydride (BPDA) 24.18g And 6.58 g of pyromellitic dianhydride (PMDA), the stirring speed was adjusted to 300 r / min, stirring was continued, and the reaction was stopped after 3 hours.

The polylysine solution obtained above was coated on a copper foil manufactured by Nippon Mining Co., Ltd., model: BHY22BT, thickness 18um, and then baked at 160 ° C for 10 minutes, and sequentially under the protection of nitrogen at 120 ° C, 160 After heating at °C, 200 ° C, 250 ° C, 300 ° C and 380 ° C for 20 minutes, the poly-proline can be amidated to form a polyimide film, and the film thickness is 25 μm to obtain a non-adhesive soft copper foil substrate.

(Example 6)

In a 500 ml reactor equipped with a water jacket, 200 ml of the solvent dimethylacetamide (DMAC) was added, and the mixture was uniformly stirred at a rate of 200 r/min, and 3,5-diamino-1,2,4-triazo was slowly added. 1.00 g of benzene (DATA) 9.20 g and 3.70 g of 4,4'-diaminobenzophenone were added to the reactor at a temperature of 20 ° C, stirred for 2 hours, and then benzophenone tetracarboxylic dianhydride (BTDA) was slowly added. 18.00 g and 6.58 g of pyromellitic dianhydride (PMDA) were stirred at a stirring speed of 300 r/min, and the reaction was stopped after 3 hours.

The polylysine solution obtained above was coated on a copper foil manufactured by Nippon Mining Co., Ltd., model: BHY22BT, thickness 18um, and then baked at 160 ° C for 10 minutes, and sequentially under the protection of nitrogen at 120 ° C, 160 After heating at °C, 200 ° C, 250 ° C, 300 ° C and 380 ° C for 20 minutes, the poly-proline can be amidated to form a polyimide film, and the film thickness is 25 μm to obtain a non-adhesive soft copper foil substrate.

(test methods)

Each of the non-adhesive soft copper foil substrates of Examples 1 to 6 was measured. The specific measurement method was as follows: 1. Peel strength, and the peel strength was tested according to the IPC-TM-6502.4.9 method by the following manner: The soft copper foil substrate is then etched into a 0.375 mm wide line, and the minimum force required to peel the copper foil at a speed of 50 mm/min is measured at a temperature of 90 degrees from the surface of the polyimide film at normal temperature, and the force is used. Except for 0.375, the peel strength value can be obtained; 2. Solder heat resistance, solder heat resistance is tested according to IPC-TM-650 2.4.13 method, and the adhesive-free soft copper foil substrate is cut into 5 cm × 5 cm sample at 400 ° C The electrode was immersed in the bath for 10 seconds to observe whether it was layered or not. 3. Curl appearance, the curl before and after etching was tested according to the IPC-TM-650 2.4.22 method, and the non-adhesive soft copper foil substrate was cut into 25 cm × 25 cm samples. Place it on a vertical plane and measure the distance between the four corners with a ruler. The four values obtained are added together, and the curl value is judged to be the curl value. If it is less than 9 cm, it is considered to be flat. The above test results are shown in Table 1.

Table 1

Table 1 BPDA: biphenyltetracarboxylic dianhydride; BTDA: benzophenone tetracarboxylic dianhydride; PMDA: pyromellitic dianhydride; DATA: triazabenzene diamine; ODA: diamine Diphenyl ether. Table 1 shows the contents of the respective components in the respective examples and the properties of the non-adhesive soft copper foil substrate in each of the examples. It can be seen from the data in Table 1 that the product of the invention has the advantages of good appearance, high heat resistance, high adhesion, high flatness and good light transmission.

The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the invention, and other equivalent variations of the patent spirit of the present invention are all within the scope of the invention.

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Claims (8)

A polyamidene adhesive which is obtained by copolymerizing a reactant comprising the following monomers selected from the group consisting of tetracarboxylic dianhydride and aromatic diamine: (a) triazabenzene diamine; (b) a pyromellitic dianhydride; and (c) a diaminodiphenyl ether, wherein the weight ratio of the tetracarboxylic dianhydride to the aromatic diamine is 1:0.7-1.3, and the triazabenzene diamine The content is less than 70% of the amine group. The polyimine adhesive according to claim 1, which further comprises a biphenyltetracarboxylic dianhydride or a benzophenone tetracarboxylic dianhydride. The polyimine adhesive according to claim 2, wherein the molar ratio of the biphenyltetracarboxylic dianhydride to the pyromellitic dianhydride is 1:0.2-5. The polyimine adhesive according to claim 2, wherein the molar ratio of benzophenonetetracarboxylic dianhydride to pyromellitic dianhydride is 1:0.2-5. The polyimine adhesive according to claim 1, further comprising 4,4'-diaminobenzophenone and 4,4'-diaminodiphenyl ether. The polyimine adhesive according to claim 5, wherein the molar ratio of the triazabenzenediamine to the 4,4'-diaminobenzophenone is 1:0.2-5. The polyimine adhesive according to claim 5, wherein the molar ratio of the triazabenzenediamine to the 4,4'-diaminodiphenyl ether is 1:0.2-5. The polyamidiamine adhesive according to claim 1, wherein the triazabenzene diamine is 3,5-diamino-1,2,4-triazabenzene.