CN112373150A - Preparation method of glue-free single-sided flexible copper-clad plate based on coating method - Google Patents

Preparation method of glue-free single-sided flexible copper-clad plate based on coating method Download PDF

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Publication number
CN112373150A
CN112373150A CN202011261326.1A CN202011261326A CN112373150A CN 112373150 A CN112373150 A CN 112373150A CN 202011261326 A CN202011261326 A CN 202011261326A CN 112373150 A CN112373150 A CN 112373150A
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temperature
thermoplastic polyimide
precursor solution
flexible copper
pressing
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陈颖
卢亢
马荔
高建宾
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XI'AN AEROSPACE SUNVALOR CHEMICAL CO Ltd
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XI'AN AEROSPACE SUNVALOR CHEMICAL CO Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

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  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Laminated Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention discloses a preparation method of a glue-free single-sided flexible copper clad laminate based on a coating method, which comprises the steps of firstly coating a layer of thermoplastic polyimide precursor solution on a polyimide film in a thin way, drying and forming a dry film which is not imidized, then coating a copper foil on the thermoplastic polyimide film for pressing after high-temperature treatment, and curing at high temperature after pressing to prepare the glue-free single-sided flexible copper clad laminate; the preparation method of the thermoplastic polyimide precursor solution comprises the steps of dissolving 8-10% by mass of diamine compounds in a solvent, and adding tetracarboxylic anhydride compounds for three times; the polyimide precursor solution was obtained by cooling with ice water and reacting for a while under a nitrogen atmosphere. The structure of the flexible copper clad laminate without glue prepared by the method is Cu/TPI/PI, only one-time high-temperature heat treatment is needed in the working procedure, the high temperature is not more than 300 ℃, the process is simple, and the cost is reduced; the folding resistance of the product is improved, and the product has high peel strength and higher dimensional stability.

Description

Preparation method of glue-free single-sided flexible copper-clad plate based on coating method
Technical Field
The invention belongs to the technical field of copper-clad plates, relates to preparation of the copper-clad plates, and particularly relates to a preparation method of a glue-free single-sided flexible copper-clad plate based on a coating method.
Background
In recent years, along with the high performance and miniaturization of digital cameras, digital video cameras, car navigators, computer accessories and other electronic products, and the appearance of high-end electronic products such as tablet computers, smart phones and the like, electronic circuits therein are developing towards the trend of being light, thin, short and small. The traditional rigid copper clad laminate does not have flexibility, and the electronic circuit produced by the rigid copper clad laminate cannot be bent and assembled, is large in size and cannot meet the actual requirements. The double-sided flexible copper clad laminate with high density, multilayering, high heat resistance and high dimensional stability is gradually replacing the rigid copper clad laminate, and becomes the mainstream of the market.
The traditional glue layer with three layers of glue plates has thick glue, and can not meet the requirements of thinning, flexibility and the like of the copper-clad plate. In addition, the adhesive with low heat resistance is used in the production, so that the performances such as heat resistance, soldering stability and the like cannot be met, and the adhesive is easy to delaminate, blister and the like when used at high temperature. And the two layers of non-adhesive plates are all subjected to high-temperature heat treatment for high-temperature imidization, so that the cost is higher.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of a glue-free single-sided flexible copper-clad plate based on a coating method.
In order to realize the task, the invention adopts the following technical solution:
a method for preparing a non-adhesive single-sided flexible copper clad laminate based on a coating method is characterized in that a layer of thermoplastic polyimide precursor solution is thinly coated on a polyimide film, a dry film which is not imidized is formed after drying, a copper foil is covered on the thermoplastic polyimide film for pressing after high-temperature treatment, and the non-adhesive single-sided flexible copper clad laminate is prepared after high-temperature curing after pressing;
the preparation method of the thermoplastic polyimide precursor solution comprises the steps of dissolving 8-10% by mass of diamine compounds in a solvent, and adding tetracarboxylic anhydride compounds for three times; the polyimide precursor solution was obtained by cooling with ice water and reacting for a while under a nitrogen atmosphere.
According to the invention, the molar ratio of the diamine compound to the tetracarboxylic anhydride compound is (0.95-1.05): (0.90-1.20); the reaction time under the condition of ice water cooling and nitrogen atmosphere is 3-8 h.
Further, the diamine compound is one or two of 4, 4 '-diaminodiphenyl ether (4, 4' -ODA) and 3,4 '-diaminodiphenyl ether (3, 4' -DAPE).
Preferably, the tetracarboxylic anhydride compound is selected from one or two of 4, 4 ' -terephthaloyl diphthalic anhydride (TDPA) and 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride (BPDA).
Further preferably, the solvent is one or two selected from N, N-Dimethylacetamide (DMAC) and N, N-Dimethylformamide (DMF).
The drying temperature is 60-200 ℃, and the drying time is 3-10 min.
The high-temperature treatment condition is imidization at 180-380 ℃ for 10-60 min.
The copper foil is covered on the polyimide film for pressing, the pressure is 10 Bar-30 Bar, the pre-pressing time is 10 s-30 s, the pressing time is 60 s-100 s, and the pressing temperature is 180 ℃.
The high-temperature curing conditions are as follows: the temperature is 120-180 ℃, and the curing time is 70-90 min.
The thickness of the prepared adhesive-free single-sided flexible copper clad laminate is 25-50 mu m, the thickness of the used polyimide film is 12-5 mu m, the thickness of the thermoplastic polyimide precursor solution thinly coated on the polyimide film is 2-6 mu m, and the copper foil is an electrolytic copper foil or a rolled copper foil and has the thickness of 12-18 mu m.
The flexible copper clad laminate without glue prepared by the method has the structure of Cu/TPI/PI, does not need too high temperature and too long time in the imidization procedure, only needs one-time high-temperature heat treatment in the procedure, has the characteristics of high peeling strength and higher dimensional stability, has simple process, reduces the thickness of the product and improves the folding resistance of the product, and the high temperature is not more than 300 ℃.
Further, since the thermoplastic polyimide solution is synthesized by copolymerization using 4, 4 ' -diaminodiphenyl ether (4, 4 ' -ODA), 3,4 ' -diaminodiphenyl ether (3, 4 ' -DAPE), 4, 4 ' -terephthaloyl diphthalic anhydride (TDPA) and 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride (BPDA) having a twisted non-coplanar structure, which have a flexible group (ketone group, ether bond) and a twisted non-coplanar structure, it is possible to adjust PI structure and properties, and 4, 4' -terephthaloyl diphthalic anhydride (TDPA) is a diketone structure with a triangular cone shape, so that the close packing of a molecular chain can be prevented, the flexibility of the molecular chain is improved, the processability of PI is improved, and the glass transition temperature is reduced. And the aromatic ketone group has a large bonding energy and can maintain excellent heat resistance. And 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) can be used to improve the dimensional stability of products because of its rigid structure.
Detailed Description
In order to clearly understand the technical features, objects and advantages of the present invention, the present invention is further described in detail with reference to the following embodiments, which are preferred examples, and the present invention is not limited to these embodiments.
The embodiment provides a preparation method of a glue-free single-sided flexible copper-clad plate based on a coating method, wherein the glue-free single-sided flexible copper-clad plate based on the coating method is composed of a thermoplastic polyimide solution, polyimide and a copper foil. The preparation method comprises the following steps:
firstly, thinly coating a layer of thermoplastic polyimide precursor solution on a polyimide film, drying and forming an imidized dry film, after high-temperature treatment, covering a copper foil on the thermoplastic polyimide film for pressing, and curing at high temperature after pressing to prepare a glue-free single-sided flexible copper-clad plate;
the preparation method of the thermoplastic polyimide precursor solution comprises the steps of dissolving 8-10% by mass of diamine compounds in a solvent, and adding tetracarboxylic anhydride compounds for three times; the polyimide precursor solution was obtained by cooling with ice water and reacting for a while under a nitrogen atmosphere.
In the present embodiment, the molar ratio of the diamine compound to the tetracarboxylic anhydride compound is (0.95 to 1.05): (0.90-1.20); the reaction time under the condition of ice water cooling and nitrogen atmosphere is 3-8 h.
The diamine compound is one or two of 4, 4 '-diaminodiphenyl ether (4, 4' -ODA) and 3,4 '-diaminodiphenyl ether (3, 4' -DAPE).
The tetracarboxylic anhydride compound is one or two of 4, 4 ' -terephthaloyl diphthalic anhydride (TDPA) and 3, 3 ', 4, 4 ' -biphenyl tetracarboxylic dianhydride (BPDA).
The solvent is one or two of N, N-Dimethylacetamide (DMAC) and N, N-Dimethylformamide (DMF), and the dosage is 200-400 ml.
The drying condition is 60-200 ℃, and the drying time is 3-10 min.
The high-temperature treatment condition is imidization for 10-30min at 180-280 ℃.
The copper foil is coated on the polyimide film for pressing under the following conditions: the pressure is 10 Bar-30 Bar, the pre-pressing time is 10-30s, the pressing time is 60-100s, and the pressing temperature is 180 ℃.
The high-temperature curing conditions are as follows: the temperature is 120-180 ℃, and the curing time is 70-90 min.
The thickness of the prepared adhesive-free single-sided flexible copper clad laminate is 25-50 mu m, the thickness of the polyimide film is 12-5 mu m, the thickness of a thermoplastic polyimide precursor solution (dry film) thinly coated on the polyimide film is 2-6 mu m, and the copper foil is an electrolytic copper foil or a rolled copper foil and has the thickness of 12-18 mu m.
The following are specific examples given by the inventors.
Example 1:
preparing a thermoplastic polyimide precursor solution: 10g of 3,4 '-diaminodiphenyl ether (hereinafter referred to as 3, 4' -DAPE), 10g of 4, 4 '-diaminodiphenyl ether (4, 4' -ODA) and 300ml of Dimethylacetamide (DMAC) were taken and added to a three-necked flask, stirred at room temperature, and after 3,4 '-DAPE was completely dissolved, 21.3g of 4, 4' -terephthaloyl diphthalic anhydride (TDPA) and 14.7g of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) were added in three portions, and copolymerization was carried out for 4 hours under ice water cooling and a nitrogen atmosphere to obtain a thermoplastic polyimide precursor solution (polyamic acid).
Preparing a non-adhesive single-sided flexible copper-clad plate: firstly, a layer of thermoplastic polyimide precursor solution (polyamide acid) is thinly coated on a 25 mu m polyimide film, the film is dried for 3min in a 160 ℃ oven to form an imidized dry film with the thickness of 6 mu m, the film is treated for 30min in an oxygen-free oven with the temperature of 280 ℃, then an electrolytic copper foil or a rolled copper foil is covered on the thermoplastic polyimide film for pressing at the temperature of 180 ℃, the pressure is 30Bar, the prepressing time is 30s, the pressing time is 60s, and the film is cured for 90min at the temperature of 180 ℃ after pressing, thus obtaining the non-glue single-sided flexible copper clad plate.
Example 2:
preparing a thermoplastic polyimide precursor solution: 10.1g of 3,4 '-diaminodiphenyl ether (hereinafter referred to as 3, 4' -DAPE), 10.1g of 4, 4 '-diaminodiphenyl ether (4, 4' -ODA) and 250ml of Dimethylacetamide (DMAC) were taken and charged into a three-necked flask, stirred at room temperature, and after 3,4 '-DAPE was completely dissolved, 21.2g of 4, 4' -terephthaloyl diphthalic anhydride (TDPA) and 14.8g of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) were added in three portions, and copolymerization was carried out for 6 hours under ice water cooling and nitrogen atmosphere to obtain a thermoplastic polyimide precursor solution (polyamic acid).
Preparing a non-adhesive single-sided flexible copper-clad plate: firstly, a layer of thermoplastic polyimide precursor solution (polyamide acid) is thinly coated on a 25 mu m polyimide film, the film is dried for 6min in an oven at 150 ℃ to form an imidized dry film with the thickness of 6 mu m, the film is treated for 10min at 230 ℃ in an oxygen-free oven, then an electrolytic copper foil or a rolled copper foil is covered on the thermoplastic polyimide film at 180 ℃ for pressing, the pressure is 10Bar, the pre-pressing time is 10s, the pressing time is 60s, and after the pressing, the film is cured for 70min at 180 ℃ to prepare the non-glue single-sided flexible copper clad plate.
Example 3:
preparing a thermoplastic polyimide precursor solution: 10.2g of 3,4 '-diaminodiphenyl ether (hereinafter referred to as 3, 4' -DAPE), 10.2g of 4, 4 '-diaminodiphenyl ether (4, 4' -ODA) and 350ml of Dimethylacetamide (DMAC) were taken and added into a three-necked flask, stirred at room temperature, and after 3,4 '-DAPE was completely dissolved, 21.4g of 4, 4' -terephthaloyl diphthalic anhydride (TDPA) and 14.6g of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) were added in three portions, and copolymerization was carried out for 8 hours under ice water cooling and nitrogen atmosphere to obtain polyamic acid.
Preparing a non-adhesive single-sided flexible copper-clad plate: firstly, a layer of thermoplastic polyimide precursor solution is thinly coated on a 25 mu m polyimide film, the film is dried in an oven at 160 ℃ for 4min to form an imidized dry film of 3 mu m, the film is treated at 240 ℃ in an oxygen-free oven at high temperature for 30min, then an electrolytic copper foil or a rolled copper foil is covered on the thermoplastic polyimide film at 180 ℃ for pressing, the pressure is 30Bar, the pre-pressing time is 10s, the pressing time is 60s, and the glue-free single-sided flexible copper-clad plate is prepared by curing at 180 ℃ for 80min after the pressing.
Example 4:
preparing a thermoplastic polyimide precursor solution: 10.3g of 3,4 '-diaminodiphenyl ether (hereinafter referred to as 3, 4' -DAPE), 10.3g of 4, 4 '-diaminodiphenyl ether (4, 4' -ODA) and 300ml of Dimethylacetamide (DMAC) were taken and charged into a three-necked flask, stirred at room temperature, and after 3,4 '-DAPE was completely dissolved, 21.0g of 4, 4' -terephthaloyl diphthalic anhydride (TDPA) and 14.9g of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) were added in three portions, and copolymerization was carried out for 3 hours under ice water cooling and nitrogen atmosphere to obtain a thermoplastic polyimide precursor solution (polyamic acid).
Preparing a non-adhesive single-sided flexible copper-clad plate: firstly, a layer of thermoplastic polyimide precursor solution is thinly coated on a polyimide film with the thickness of 12.5 microns, the polyimide film is dried for 10min in an oven with the temperature of 100 ℃ to form a dry film without imidization with the thickness of 3 microns, the dry film is treated for 20min in an oxygen-free oven with the temperature of 260 ℃, then an electrolytic copper foil or a rolled copper foil is covered on the thermoplastic polyimide film for pressing at the temperature of 180 ℃, the pressure is 20Bar, the prepressing time is 20s, the pressing time is 90s, and the glue-free single-sided flexible copper clad plate is prepared by curing for 70min at the temperature of 170 ℃ after pressing.
Example 5:
preparing a thermoplastic polyimide precursor solution: 9.9g of 3,4 '-diaminodiphenyl ether (hereinafter referred to as 3, 4' -DAPE), 9.9g of 4, 4 '-diaminodiphenyl ether (4, 4' -ODA) and 250ml of Dimethylacetamide (DMAC) were taken and charged into a three-necked flask, stirred at room temperature, and after 3,4 '-DAPE was completely dissolved, 21.1g of 4, 4' -terephthaloyl diphthalic anhydride (TDPA) and 14.5g of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) were added in three portions, and copolymerization was carried out for 5 hours under ice water cooling and a nitrogen atmosphere to obtain a thermoplastic polyimide precursor solution (polyamic acid).
Preparing a non-adhesive single-sided flexible copper-clad plate: firstly, a layer of thermoplastic polyimide precursor solution (polyamide acid) is thinly coated on a polyimide film with the thickness of 12.5 microns, the polyimide film is dried for 8min at the temperature of 110 ℃ to form a dry film without imidization with the thickness of 6 microns, the dry film is treated at the temperature of 270 ℃ for 20min at high temperature, then an electrolytic copper foil or a rolled copper foil is covered on the thermoplastic polyimide film at the temperature of 180 ℃ for pressing, the pressure is 15Bar, the prepressing time is 30s, the pressing time is 100s, and the glue-free single-sided flexible copper clad laminate is prepared after 180 ℃ curing for 90min after pressing.
Example 6:
preparing a thermoplastic polyimide precursor solution: 9.8g of 3,4 '-diaminodiphenyl ether (hereinafter referred to as 3, 4' -DAPE), 9.8g of 4, 4 '-diaminodiphenyl ether (4, 4' -ODA) and 300ml of Dimethylacetamide (DMAC) were taken and charged into a three-necked flask, stirred at room temperature, and after 3,4 '-DAPE was completely dissolved, 21.2g of 4, 4' -terephthaloyl diphthalic anhydride (TDPA) and 14.4g of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) were added in three portions, and reacted for 7 hours under ice water cooling and a nitrogen atmosphere to obtain a thermoplastic polyimide precursor solution (polyamic acid).
Preparing a non-adhesive single-sided flexible copper-clad plate: firstly, a layer of thermoplastic polyimide precursor solution (polyamide acid) is thinly coated on a 25 mu m polyimide film, the film is dried for 7min in a 120 ℃ oven to form an imidized dry film with the thickness of 3 mu m, the film is processed for 30min in an oxygen-free oven with the temperature of 230 ℃, then an electrolytic copper foil or a rolled copper foil is covered on the thermoplastic polyimide film for pressing at the temperature of 180 ℃, the pressure is 10Bar, the prepressing time is 30s, the pressing time is 80s, and after the pressing, the film is cured for 75min at the temperature of 175 ℃ to prepare the non-glue single-sided flexible copper clad plate.
Example 7:
preparing a thermoplastic polyimide precursor solution: 10.3g of 3,4 '-diaminodiphenyl ether (hereinafter referred to as 3, 4' -DAPE), 10.3g of 4, 4 '-diaminodiphenyl ether (4, 4' -ODA) and 250ml of Dimethylacetamide (DMAC) were taken and charged into a three-necked flask, stirred at room temperature, and after 3,4 '-DAPE was completely dissolved, 21.5g of 4, 4' -terephthaloyl diphthalic anhydride (TDPA) and 14.8g of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) were added in three portions, and copolymerization was carried out for 7.5 hours under ice water cooling and nitrogen atmosphere to obtain a thermoplastic polyimide precursor solution (polyamic acid).
Preparing a non-adhesive single-sided flexible copper-clad plate: firstly, a layer of thermoplastic polyimide precursor solution (polyamide acid) is thinly coated on a 25 mu m polyimide film, the film is dried for 6min in a 130 ℃ oven to form an imidized dry film with the thickness of 6 mu m, the film is treated for 30min at a high temperature in a 250 ℃ oxygen-free oven, then an electrolytic copper foil or a rolled copper foil is covered on the thermoplastic polyimide film for pressing at 180 ℃ with the pressure of 20Bar, the prepressing time of 20s and the pressing time of 100s, and the film is cured for 90min at 150 ℃ after pressing to prepare the non-glue single-sided flexible copper clad plate.
Example 8:
preparing a thermoplastic polyimide precursor solution: 9.7g of 3,4 '-diaminodiphenyl ether (hereinafter referred to as 3, 4' -DAPE), 9.7g of 4, 4 '-diaminodiphenyl ether (4, 4' -ODA) and 250ml of Dimethylacetamide (DMAC) were taken and charged into a three-necked flask, stirred at room temperature, and after 3,4 '-DAPE was completely dissolved, 21.1g of 4, 4' -terephthaloyl diphthalic anhydride (TDPA) and 14.5g of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) were added in three portions, and copolymerization was carried out for 6.5 hours under ice water cooling and nitrogen atmosphere to obtain a thermoplastic polyimide precursor solution (polyamic acid).
Preparing a non-adhesive single-sided flexible copper-clad plate: firstly, a layer of thermoplastic polyimide precursor solution (polyamide acid) is thinly coated on a 25 mu m polyimide film, the film is dried for 5min in an oven at 140 ℃ to form an imidized dry film of 6 mu m, the film is treated for 20min at 260 ℃ in an oxygen-free oven, then an electrolytic copper foil or a rolled copper foil is covered on the thermoplastic polyimide film at 180 ℃ for pressing, the pressure is 30Bar, the pre-pressing time is 30s, the pressing time is 90s, and the film is cured for 85min at 165 ℃ after pressing to obtain the non-glue single-sided flexible copper clad plate.
Comparative example 1:
preparing a thermoplastic polyimide precursor solution: 19.8g of 4, 4 ' -diaminodiphenylmethane (4, 4 ' -MDA) and 350ml of Dimethylacetamide (DMAC) are added into a three-necked flask, stirred at room temperature, after 3,4 ' -DAPE is completely dissolved, 29.4g of 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride (BPDA) is added in three times, and copolymerization reaction is carried out for 6.5 hours under the conditions of ice water cooling and nitrogen atmosphere, so as to obtain a thermoplastic polyimide precursor solution (polyamic acid).
Preparing a non-adhesive single-sided flexible copper-clad plate: firstly, a layer of thermoplastic polyimide precursor solution (polyamide acid) is thinly coated on a 25 mu m polyimide film, the film is dried for 3min in a 160 ℃ oven to form an imidized dry film with the thickness of 6 mu m, the film is treated for 30min in an oxygen-free oven with the temperature of 280 ℃, then an electrolytic copper foil or a rolled copper foil is covered on the thermoplastic polyimide film for pressing at the temperature of 180 ℃, the pressure is 30Bar, the prepressing time is 30s, the pressing time is 60s, and the film is cured for 90min at the temperature of 180 ℃ after pressing, thus obtaining the non-glue single-sided flexible copper clad plate.
Comparative example 2:
preparing a thermoplastic polyimide precursor solution: 19.8g of 4, 4 '-diaminodiphenylmethane (4, 4' -MDA) and 300ml of Dimethylacetamide (DMAC) were taken and added into a three-necked flask, stirred at room temperature, and when 4, 4 '-ODA was completely dissolved, 42.6g of 4, 4' -terephthaloyl diphthalic anhydride (TDPA) was added three times, and copolymerization was carried out for 6.5 hours under the conditions of ice water cooling and nitrogen atmosphere, to obtain a thermoplastic polyimide precursor solution (polyamic acid).
Preparing a non-adhesive single-sided flexible copper-clad plate: firstly, a layer of thermoplastic polyimide precursor solution (polyamide acid) is thinly coated on a 25 mu m polyimide film, the film is dried for 3min in a 160 ℃ oven to form an imidized dry film with the thickness of 6 mu m, the film is treated for 30min in an oxygen-free oven with the temperature of 280 ℃, then an electrolytic copper foil or a rolled copper foil is covered on the thermoplastic polyimide film for pressing at the temperature of 180 ℃, the pressure is 30Bar, the prepressing time is 30s, the pressing time is 60s, and the film is cured for 90min at the temperature of 180 ℃ after pressing, thus obtaining the non-glue single-sided flexible copper clad plate.
Comparative example 3:
two layers of electrolytic copper foil with the thickness of 12 mu m are pressed on two sides of a polyimide composite film (trade name SP1-350F, Yinxi engineering plastics Co., Ltd.) with the thickness of 25 mu m by a high-temperature roll squeezer with the roll temperature of 360 ℃ to obtain the non-adhesive double-sided flexible copper clad laminate.
Comparative example 4:
two layers of electrolytic copper foil with the thickness of 12 mu m are pressed on two sides of a polyimide composite film (trade name TPI 50KN, DuPont company in America) with the thickness of 25 mu m by a high-temperature roll squeezer with the roll temperature of 360 ℃ to obtain the non-adhesive double-sided flexible copper clad laminate.
The following tables 1 and 2 show the performance parameters of the non-adhesive single-sided flexible copper clad laminate obtained in examples 1 to 8. The performance parameters of the non-adhesive flexible copper clad laminate of the comparative example are given in table 3.
Table 1: comparison of Performance parameters of non-adhesive Flexible copper clad laminate
Figure BDA0002774733660000101
Figure BDA0002774733660000111
Table 2: comparison of Performance parameters of non-adhesive Flexible copper clad laminate
Figure BDA0002774733660000112
Note: the technical indexes and test standards are the same as those in Table 1.
Table 3: comparison of Performance parameters of non-adhesive Flexible copper clad laminate
Figure BDA0002774733660000113
Figure BDA0002774733660000121
Note: the technical indexes and test standards are the same as those in Table 1.
As can be seen from tables 1 and 2, the flexible copper clad laminates without adhesive prepared in examples 1 to 8 have good performance in terms of curling, peeling strength, dimensional stability, soldering heat resistance and folding endurance.
As can be seen from table 3, comparative examples 1 and 2 are inferior in both peel strength and heat resistance, and are inferior in folding resistance, i.e., inferior in flexibility. This is because the thermoplastic polyimide solutions were synthesized using a single diamine and dianhydride monomer in comparative examples 1 and 2, and the flexible groups (ketone groups, ether bonds) were small, and the flexible single faceplates prepared were poor in flexibility and low in peeling. The performance of the flexible copper clad laminate prepared in the embodiments 1 to 8 is better, and can be similar to that of the flexible copper clad laminate prepared by TPI in the market, such as the performance of each performance of the comparative example 4. This is because in this example, the inventors introduced a flexible group (ketone group, ether bond) and a twisted non-coplanar structure into a solution for synthesizing a thermoplastic polyimide by a copolymerization method, and were able to adjust the PI structure and properties. The 4, 4' -terephthaloyl diphthalic anhydride (TDPA) has a triangular-cone-shaped diketone-base structure, can prevent the tight packing of a molecular chain, improve the flexibility of the molecular chain, improve the processability of PI, reduce the glass transition temperature and further reduce the cost. The bond energy of the aryl ketone group is large, so that excellent heat resistance can be maintained; and 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) can be used to improve the dimensional stability of products because of its rigid structure.
In summary, the method for preparing the non-adhesive single-sided flexible copper clad laminate based on the coating method provided by the embodiment has the advantages that the structure of the prepared non-adhesive single-sided flexible copper clad laminate is Cu/TPI/PI, the product does not need too high temperature and too long time in the imidization process, only one high-temperature heat treatment is needed in the process, the high temperature is not more than 300 ℃, the cost is reduced, and the non-adhesive single-sided flexible copper clad laminate has the characteristics of high peel strength and higher dimensional stability. Meanwhile, the process is simple, the thickness of the product is reduced, and the folding resistance of the product is improved.
Further, since the thermoplastic polyimide solution is synthesized by copolymerization using 4, 4 ' -diaminodiphenyl ether (4, 4 ' -ODA), 3,4 ' -diaminodiphenyl ether (3, 4 ' -DAPE), 4, 4 ' -terephthaloyl diphthalic anhydride (TDPA) and 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride (BPDA) having a twisted non-coplanar structure, which have a flexible group (ketone group, ether bond) and a twisted non-coplanar structure, it is possible to adjust PI structure and properties, and 4, 4' -terephthaloyl diphthalic anhydride (TDPA) is a diketone structure with a triangular cone shape, so that the close packing of a molecular chain can be prevented, the flexibility of the molecular chain is improved, the processability of PI is improved, and the glass transition temperature is reduced. And the aromatic ketone group has a large bonding energy and can maintain excellent heat resistance. And 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) can be used to improve the dimensional stability of products because of its rigid structure.

Claims (10)

1. A method for preparing a non-adhesive single-sided flexible copper clad laminate based on a coating method is characterized in that a layer of thermoplastic polyimide precursor solution is thinly coated on a polyimide film, a dry film which is not imidized is formed after drying, a copper foil is covered on the thermoplastic polyimide film for pressing after high-temperature treatment, and the non-adhesive single-sided flexible copper clad laminate is prepared after high-temperature curing after pressing;
the preparation method of the thermoplastic polyimide precursor solution comprises the steps of dissolving 8-10% by mass of diamine compounds in a solvent, and adding a tetracarboxylic anhydride compound B for three times; the polyimide precursor solution was obtained by cooling with ice water and reacting for a while under a nitrogen atmosphere.
2. The method according to claim 1, wherein the molar ratio of the diamine compound to the tetracarboxylic anhydride compound is (0.95 to 1.05): (0.90-1.20); the reaction time under the condition of ice water cooling and nitrogen atmosphere is 3-8 h.
3. The method of claim 1, wherein the diamine compound is selected from one or two of para-4, 4 '-diaminodiphenyl ether (4, 4' -ODA), 3,4 '-diaminodiphenyl ether (3, 4' -DAPE).
4. The method according to claim 1, wherein the tetracarboxylic anhydride compound is selected from one or both of 4, 4 ' -terephthaloyl diphthalic anhydride (TDPA) and 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride (BPDA).
5. The method of claim 1, wherein the solvent is selected from one or both of N, N-Dimethylacetamide (DMAC), N-Dimethylformamide (DMF).
6. The method of claim 1, wherein the drying temperature is 60 ℃ to 200 ℃ and the drying time is 3min to 10 min.
7. The method of claim 1, wherein the high temperature treatment conditions are 180 ℃ to 380 ℃ imidization for 10min to 60 min.
8. The method of claim 1, wherein the copper foil is laminated on the thermoplastic polyimide film at a laminating temperature of 180 ℃, a pressure of 10Bar to 30Bar, a pre-pressing time of 10s to 30s, and a laminating time of 60s to 100 s.
9. The method of claim 1, wherein the high temperature aging conditions are: the temperature is 120-180 ℃, and the curing time is 70-90 min.
10. The method of claim 1, wherein the prepared non-adhesive single-sided flexible copper clad laminate has a thickness of 25 to 50 μm, the polyimide film used has a thickness of 12 to 5 μm, the thermoplastic polyimide precursor solution thinly coated on the polyimide film has a thickness of 2 to 6 μm, and the copper foil is an electrolytic copper foil or a rolled copper foil having a thickness of 12 to 18 μm.
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