Preparation method of non-curling high-adhesiveness glue-free flexible copper-clad plate

A flexible copper clad laminate, high viscosity technology, used in chemical instruments and methods, improvement of metal adhesion of insulating substrates, devices for coating liquid on surfaces, etc., can solve peeling product cracks, affecting product performance, polyimide Amine coating and copper foil curling, etc., to achieve excellent mechanical properties and heat resistance, improve dimensional stability, and good dimensional stability.

Inactive Publication Date: 2010-04-14
SICHUAN UNIV
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AI Technical Summary

Problems solved by technology

Its disadvantages are: it is difficult to produce on a large scale due to numerous processes, and the production cost is high, and ultra-thin flexible copper clad laminates cannot be obtained (Xinshi Gu et al., Printed Circuit Information, 2004, 4: 29-33)
[0007] Even so, for the direct coating method, there are still two problems to be solved: on the one hand, it is necessary to reduce the linear thermal expansion coefficient of the polyimide resin coating coated on the copper foil, so that it is linear with the copper foil. The thermal expansion coefficients are roughly equivalent (because the internal thermal stress of the product caused by the excessive difference between the two thermal expansion coefficients will cause the polyimide coating and copper foil to curl, or even peel off or crack the product, which will seriously affect the product performance). For products with high dimensional stability, solve the curling phenomenon that occurs during molding or processing; on the other hand, it is necessary to improve the bonding strength between the polyimide resin coating on the copper foil and the copper foil
These two problems are a pair of contradictory opposites, because generally speaking, the rigid polyimide molecular chain may have a low linear thermal expansion coefficient, but the rigid polyimide resin is compatible with the copper foil. Adhesion is not ideal
In order to solve this contradiction, the "multi-coating" process method (also known as multi-layer coating method) is disclosed in the Japanese Patent Laid-Open No. 8-250860. Its working principle is similar to that of the lamination method. , plays a different role), although it not only solves the dimensional stability problem of flexible copper clad laminate (FCCL), but also makes the copper foil and the resin layer have strong adhesion, but the product molding process is extremely complicated, and the production efficiency Low, so the production cost is extremely high, and the coating is thick, it is difficult to obtain ultra-thin flexible copper clad laminates

Method used

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  • Preparation method of non-curling high-adhesiveness glue-free flexible copper-clad plate
  • Preparation method of non-curling high-adhesiveness glue-free flexible copper-clad plate
  • Preparation method of non-curling high-adhesiveness glue-free flexible copper-clad plate

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Experimental program
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Effect test

Embodiment 1

[0041] According to the ratio of BTDA: 5p-BOA: 6p-BOA: 4-BABP=100: 40: 20: 40, the three aromatic diamine monomers of 5p-BOA, 6p-BOA and 4-BABP Add NMP, and stir until dissolved under nitrogen atmosphere, then add BTDA and continue to stir, make it polymerize at 0°C in nitrogen atmosphere for 70 hours, and obtain a viscous polyamic acid homogeneous solution with a solid content of 10wt%. . Its intrinsic viscosity is 1.90dL / g.

[0042] Firstly, the obtained polyamic acid glue is coated on a rolled copper foil with a thickness of 6 microns, and then baked at 150°C for 5 minutes, and the thickness of the coating is controlled to be 10-15 µm after the solvent evaporates, and then dried in a vacuum oven. In the process, step-by-step thermal curing is carried out at 80°C, 120°C, 180°C, 220°C, and 380°C for 30 minutes each in sequence, and an adhesive-free flexible copper-clad laminate with no curl and high dimensional stability is obtained.

Embodiment 2

[0044] According to the ratio of BTDA: 6m-BOA: 4-BABP = 100: 40: 60 according to the amount of substances, first add 6m-BOA and 4-BABP two aromatic diamine monomers into DMAc, and stir under nitrogen atmosphere After dissolving, BTDA was added and stirred continuously, and polymerized at 20° C. for 24 hours in a nitrogen atmosphere to obtain a viscous polyamic acid homogeneous solution with a solid content of 15 wt%. Its intrinsic viscosity is 1.28dL / g.

[0045] Firstly, the obtained polyamic acid glue is coated on a rolled copper foil with a thickness of 9 microns, and then baked at 120°C for 60 minutes, and the thickness of the coating is controlled to be 15-20 µm after the solvent evaporates. In the high-temperature drying tunnel, step-by-step thermal curing is carried out at 80°C, 120°C, 180°C, 280°C, and 340°C for 60 minutes each, so that a non-adhesive flexible copper-clad laminate with no curl and high dimensional stability can be obtained .

Embodiment 3

[0047] According to the ratio of BTDA: 5p-BOA: 4-BABP: 3, 4'-ODA=100: 90: 5: 5 according to the amount of substances, first mix 5p-BOA, 4-BABP and 3, 4'-ODA Add a kind of aromatic diamine monomer into DMAc, and stir until dissolved under a nitrogen atmosphere, then add BTDA and continue to stir, make it polymerize at 20°C for 24 hours in a nitrogen atmosphere, and obtain a viscous mixture with a solid content of 18wt%. Polyamic acid homogeneous solution. Its intrinsic viscosity is 1.74dL / g.

[0048] First coat the obtained polyamic acid glue on a rolled copper foil with a thickness of 12 microns, then bake it at 140°C for 70 minutes, and control the thickness of the coating to 20-25 µm after the solvent evaporates, and then heat it in a vacuum oven. In the process, step-by-step thermal curing is carried out at 80°C, 120°C, 180°C, 260°C, and 380°C for 10 minutes each in sequence, and an adhesive-free flexible copper-clad laminate with no curl and high dimensional stability is ...

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Abstract

The invention discloses a direct coating method for preparing a non-curling high-adhesiveness glue-free flexible copper-clad plate. The method comprises the following steps: firstly, dissolving an aromatic diamine monomer containing a benzoxazole structure, an aromatic diamine monomer containing a keto ether structure, an aromatic diamine monomer containing a full-ether link structure and an aromatic dianhydride monomer in an aprotic polar solvent to prepare a polyamic acid glue solution by a polymerization; then, coating the polyamic acid glue solution on a copper foil with the thickness of 6-35 microns; baking at 50-150 DEG C for 5-180 minutes; then, arranging in a vacuum oven or a high-temperature drying tunnel in nitrogen atmosphere for phasic thermocuring respectively at 80 DEG C, 120 DEG C, 180 DEG C, 220-280 DEG C and 320-380 DEG C, wherein each thermocuring phase keeps 10-90 minutes. The glue-free flexible copper-clad plate prepared by the method not only has high adhesiveness, no curling and high peeling strength, but also has excellent chemical performance, heat resistance, favorable bending resistance and lower water-absorbing rate. The method has once coating molding, simple preparation process and lower production cost.

Description

technical field [0001] The invention belongs to the technical field of preparing glue-free flexible copper-clad laminates by direct coating, in particular to a glue-free flexible copper-clad laminate with no curl, high adhesiveness and dimensional stability prepared by direct coating with polyamic acid glue. copper plate method. Background technique [0002] With the rapid development of high-performance, high-density and integrated electronic products, the flexible copper-clad laminate as its base material is also constantly following this development trend, that is, it has improved in terms of its size thinning and stability. With the development and improvement to a great extent, the printed circuit industry has also successively developed adhesive-free two-layer flexible copper-clad laminates (2L-FCCL) with thin thickness and excellent comprehensive performance, which meets the needs of high-performance electronic products to a certain extent. demand. At present, there...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H05K3/38C08L79/08C08G73/10B05D7/16B05D3/02B32B15/088B32B15/20
Inventor 顾宜庄永兵刘向阳朱蓉琪盛兆碧
Owner SICHUAN UNIV
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