Circuit board low-profile coarsened copper foil and application thereof

Abstract

The invention relates to the technical field of circuit boards, in particular to a low-profile coarsened copper foil for a circuit board and application of the low-profile coarsened copper foil for the circuit board, and the low-profile coarsened copper foil adopts a two-coarsening and one-solidifying treatment process and comprises the following steps: adding indium and cerium elements and hydroxyethyl cellulose with the molecular weight of 80,000-100,000 into coarsening liquid; the components in the silane treatment liquid are limited, and imidazole amide propyl triethoxy silane is used as a coupling agent to react with tetraethyl silicate and modified bisphenol A polyaryletherketone under the catalysis of ammonia water; the imidazole amide propyl triethoxy silane is synthesized by taking imidazole and gamma-isocyanate propyl triethoxy silane as raw materials; the preparation method of the modified bisphenol A type polyaryletherketone comprises the following steps: synthesizing a monomer containing an imide phenoxy hexafluoropropane structure by using 2, 2-bis [4-(4-aminophenoxy benzene)] hexafluoropropane and 4-chlorophthalic anhydride as raw materials, copolymerizing the monomer with bisphenol A and 4, 4 '-difluorobenzophenone, and introducing an imide phenoxy hexafluoropropane group on a main chain structure of the polyaryletherketone.

Description

Technical Field

[0001] The invention relates to the technical field of circuit boards, in particular to a low-profile roughened copper foil for a circuit board and application thereof. Background Art

[0002] As the basic carrier for signal transmission, circuit boards are widely used in communications, aerospace and other fields. Circuit boards are generally made by laminating metal substrates with resin films and etching to form circuit patterns. Copper-based materials are often used as raw materials for circuit board preparation due to their good dielectric constants. With the surge in demand for 5G substrates, the demand for high-frequency and high-speed circuit boards is also increasing.

[0003] In traditional circuit boards, the inner copper surface is mostly treated with browning, which is done by etching the copper surface to produce a rough morphology, thereby improving the bonding strength between the copper surface and the resin. However, the electromagnetic interference and skin effect on the rough surface are not conducive to the high-frequency signal transmission of the printed circuit board. Existing chemical interface enhancements mostly use silane coupling agents to anchor the copper surface, which has the advantages of strong modifiability and mild operating conditions, but also has defects such as poor high temperature resistance and limited water resistance. Summary of the invention

[0004] The object of the present invention is to provide a low-profile roughened copper foil for a circuit board and its application to solve the problems raised in the prior art.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] A production process for a low-profile roughened copper foil for a circuit board, comprising the following steps:

[0007] S1: placing the copper foil in a pickling solution for pickling treatment to obtain a pickled copper foil;

[0008] S2: preparing a roughening solution with sulfuric acid, copper sulfate, hydrochloric acid, indium sulfate, cerous sulfate, and hydroxyethyl cellulose, placing the pickled copper foil in the roughening solution, and performing two roughening treatments to obtain a roughened copper foil;

[0009] S3: subjecting the roughened copper foil to curing treatment, high temperature anti-oxidation treatment, and room temperature anti-oxidation treatment to obtain a pretreated copper foil;

[0010] S4: spraying the pretreated copper foil with a silane treatment solution, and drying the pretreated copper foil to obtain a low-profile roughened copper foil for a circuit board.

[0011] Furthermore, the working conditions of the pickling treatment are: temperature of 25-40°C, time of 5-10s; the composition of the pickling solution is: deionized water as solvent, containing 100-170g / L sulfuric acid and 2-5g / L copper sulfate.

[0012] Furthermore, the working conditions of the curing treatment are: current density 15-20A / dm 2 , temperature 35-45°C, time 5-10s; the composition of the solidifying liquid is: deionized water as solvent, containing 80-140g / L sulfuric acid and 35-50g / L copper sulfate.

[0013] Furthermore, the working conditions of the roughening treatment are: current density 20-30A / dm 2 , temperature 25-35℃, time 10-20s; the composition of the roughening solution is: deionized water as solvent, containing 160-180g / L sulfuric acid, 8-20g / L copper sulfate, 15-30mg / L hydrochloric acid, 10-30mg / L indium sulfate, 20-50mg / L cerium sulfate, and 10-20mg / L hydroxyethyl cellulose.

[0014] Furthermore, the working conditions of high temperature anti-oxidation treatment are: current density 5-10A / dm 2 , temperature 35-45℃, time 5-10s; high temperature anti-oxidation treatment liquid composition: deionized water as solvent, containing potassium pyrophosphate 85-110g / L, zinc sulfate 2.5-4.5g / L, nickel sulfate 0.1-0.5g / L, pH value 8.5-9.5; room temperature anti-oxidation treatment working conditions: current density 5-10A / dm 2 , temperature 25-35℃, time 5-10s; the composition of the room temperature anti-oxidation treatment liquid is: deionized water as solvent, containing 2-3g / L potassium dichromate.

[0015] Furthermore, the working conditions of the drying treatment are: keeping warm at 160-220° C. for 6-10 seconds.

[0016] Further, the preparation of the silane treatment solution comprises the following steps:

[0017] Imidazole amidopropyl triethoxysilane, tetraethyl silicate, modified bisphenol A type polyaryletherketone, N,N-dimethylacetamide and deionized water are mixed, ultrasonically treated at 45kHz for 20-30min, ammonia water is added, stirred for 1-2h to obtain a silane treatment agent, and deionized water is added to mix to obtain a silane treatment solution.

[0018] Furthermore, deionized water is used as a solvent, and the silane treatment liquid contains 0.8-1.5 g / L of a silane treatment agent; the raw material composition of the silane treatment agent is, by mass, 3-6 parts of imidazole amide propyl triethoxysilane, 1-2 parts of tetraethyl silicate, 2-4 parts of modified bisphenol A type polyaryletherketone, 33-44 parts of N,N-dimethylacetamide, 3-5 parts of deionized water, and 0.2-0.5 parts of ammonia water.

[0019] Further, the preparation of imidazole amidopropyl triethoxysilane comprises the following steps:

[0020] Under nitrogen protection, imidazole and tetrahydrofuran were mixed, the temperature was raised to 48-52°C, γ-isocyanatepropyltriethoxysilane was added, stirred for 110-130 minutes, reduced pressure, and separated by column with acetone and petroleum ether in a volume ratio of 4:6 to obtain imidazoleamidopropyltriethoxysilane.

[0021] Further, the preparation of the modified bisphenol A type polyaryletherketone comprises the following steps:

[0022] 1) Under nitrogen protection, 2,2-bis[4-(4-aminophenoxybenzene)]hexafluoropropane, 4-chlorophthalic anhydride and toluene are mixed, heated to 118-122°C and kept for 230-250 min, heated to 143-147°C and kept for 50-70 min, heated to 158-162°C and kept for 50-70 min, discharged in anhydrous ethanol, washed with toluene 3-4 times, filtered and dried to obtain bischloroimidephenoxyhexafluoropropane;

[0023] 2) Under nitrogen protection, bisphenol A, 4,4'-difluorobenzophenone and bis(chloroimide)phenoxyhexafluoropropane are mixed, sulfolane, sodium carbonate and p-xylene are added in sequence, the temperature is raised to 168-172°C and kept for 3-4 hours, the temperature is raised to 178-182°C and kept for 1-2 hours, the temperature is raised to 218-222°C and kept for 2-3 hours, the material is poured into deionized water, dried and crushed, washed with deionized water and anhydrous ethanol by boiling for 6-8 times in sequence, filtered and dried to obtain modified bisphenol A type polyaryletherketone.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The present invention provides a low-profile roughened copper foil for a circuit board and application thereof. Through composition and process design, a low-profile roughened copper foil with corrosion resistance, high temperature resistance, water resistance and high peeling strength is prepared to meet the requirements of high-frequency and high-speed circuit boards.

[0026] The present invention adopts a two-roughening and one-solidifying treatment process to greatly improve the surface roughness of the copper foil and enhance its peeling strength. During the two roughening treatments, indium and cerium elements and hydroxyethyl cellulose with a molecular weight of 80,000 to 100,000 are added to the roughening solution to make the copper foil roughness lower than 2 μm, while enhancing the corrosion resistance and oxidation resistance of the copper foil.

[0027] In order to further improve the corrosion resistance of the copper foil surface and give it high temperature resistance and water and anti-fouling properties, the components in the silane treatment liquid are limited, and imidazole amide propyl triethoxysilane is used as a coupling agent. It is reacted with tetraethyl silicate and modified bisphenol A type polyaryletherketone under the catalysis of ammonia water to construct a complex cross-linked network, thereby giving the copper foil low surface energy and high temperature resistance.

[0028] Imidazole amide propyl triethoxysilane is synthesized with imidazole and γ-isocyanate propyl triethoxysilane as raw materials. Imidazole is used as a corrosion inhibitor to hybridize with a silane coupling agent, thereby further improving the corrosion resistance of the copper foil and making the formed film tighter and smoother. Modified bisphenol A type polyaryletherketone is synthesized by first using 2,2-bis[4-(4-aminophenoxybenzene)]hexafluoropropane and 4-chlorophthalic anhydride as raw materials to prepare a monomer containing an imidophenoxyhexafluoropropane structure, which is then copolymerized with bisphenol A and 4,4'-difluorobenzophenone, and imidophenoxyhexafluoropropane groups are introduced into the main chain structure of polyetheretherketone, thereby further enhancing the heat resistance and water resistance of the polyaryletherketone, thereby improving the corrosion resistance, high temperature resistance, water resistance, peel strength and other properties of the roughened copper foil, so that it can meet the requirements of high-frequency and high-speed circuit boards. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a scanning electron microscope image of the copper foil prepared in Example 1. DETAILED DESCRIPTION

[0030] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] It should be noted that if the embodiments of the present invention involve directional indications such as up, down, left, right, front, and back, the directional indication is only used to explain a specific posture such as the relative position relationship between the components, the movement status, etc. If the specific posture changes, the directional indication will also change accordingly. In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the ability of ordinary technicians in this field to implement. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the protection scope required by the present invention.

[0032] The technical solution of the present invention is further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0033] Embodiment 1: A production process for a low-profile roughened copper foil for a circuit board, comprising the following steps:

[0034] S1: placing the copper foil in a pickling solution for pickling treatment to obtain a pickled copper foil;

[0035] The working conditions of pickling treatment are: temperature 40°C, time 10s, and the composition of pickling solution: deionized water as solvent, containing 170g / L sulfuric acid and 5g / L copper sulfate;

[0036] S2: preparing a roughening solution with sulfuric acid, copper sulfate, hydrochloric acid, indium sulfate, cerous sulfate, and hydroxyethyl cellulose, placing the pickled copper foil in the roughening solution, and performing two roughening treatments to obtain a roughened copper foil;

[0037] The working conditions of the roughening treatment are: current density 30A / dm 2 , temperature 35℃, time 20s; the composition of the roughening solution is: deionized water as solvent, containing 180g / L sulfuric acid, 20g / L copper sulfate, 30mg / L hydrochloric acid, 30mg / L indium sulfate, 50mg / L cerium sulfate, and 20mg / L hydroxyethyl cellulose;

[0038] S3: subjecting the roughened copper foil to curing treatment, high temperature anti-oxidation treatment, and room temperature anti-oxidation treatment to obtain a pretreated copper foil;

[0039] The working conditions of the curing treatment are: current density 20A / dm 2 , temperature 45°C, time 10s; the composition of the solidifying liquid is: deionized water as solvent, containing 140g / L sulfuric acid and 50g / L copper sulfate;

[0040] The working conditions of high temperature anti-oxidation treatment are: current density 10A / dm 2 , temperature 45℃, time 10s; high temperature anti-oxidation treatment liquid composition: deionized water as solvent, containing potassium pyrophosphate 110g / L, zinc sulfate 4.5g / L, nickel sulfate 0.5g / L, pH value 9.5; room temperature anti-oxidation treatment working conditions: current density 10A / dm 2 , temperature 35℃, time 10s; the room temperature anti-oxidation treatment solution is composed of: deionized water as solvent, containing 3g / L potassium dichromate;

[0041] S4: spraying the pretreated copper foil with a silane treatment solution, and drying the pretreated copper foil to obtain a low-profile roughened copper foil for a circuit board;

[0042] Deionized water is used as solvent, and the silane treatment liquid contains 1.5 g / L of silane treatment agent (N,N-dimethylformamide solution of γ-isocyanatepropyltriethoxysilane with a mass concentration of 50%); the working conditions of the drying treatment are: keeping warm at 220° C. for 6 seconds.

[0043] Embodiment 2: A production process for a low-profile roughened copper foil for a circuit board, comprising the following steps:

[0044] S1: placing the copper foil in a pickling solution for pickling treatment to obtain a pickled copper foil;

[0045] The working conditions of pickling treatment are: temperature 25°C, time 5s; the composition of pickling solution is: deionized water as solvent, containing 100g / L sulfuric acid and 2g / L copper sulfate;

[0046] S2: preparing a roughening solution with sulfuric acid, copper sulfate, hydrochloric acid, indium sulfate, cerous sulfate, and hydroxyethyl cellulose, placing the pickled copper foil in the roughening solution, and performing two roughening treatments to obtain a roughened copper foil;

[0047] The working conditions of the roughening treatment are: current density 20A / dm 2 , temperature 25℃, time 10s; the composition of the roughening solution is: deionized water as solvent, containing 160g / L sulfuric acid, 8g / L copper sulfate, 15mg / L hydrochloric acid, 10mg / L indium sulfate, 20mg / L cerium sulfate, and 10mg / L hydroxyethyl cellulose;

[0048] S3: subjecting the roughened copper foil to curing treatment, high temperature anti-oxidation treatment, and room temperature anti-oxidation treatment to obtain a pretreated copper foil;

[0049] The working conditions of the curing treatment are: current density 15A / dm 2 , temperature 35℃, time 5s; the composition of the solidifying liquid is: deionized water as solvent, containing 80g / L sulfuric acid and 35g / L copper sulfate;

[0050] The working conditions of high temperature anti-oxidation treatment are: current density 5A / dm 2 , temperature 35℃, time 5s; high temperature anti-oxidation treatment liquid composition: deionized water as solvent, containing potassium pyrophosphate 85g / L, zinc sulfate 2.5g / L, nickel sulfate 0.1g / L, pH value 8.5; room temperature anti-oxidation treatment working conditions: current density 5A / dm 2 , temperature 25℃, time 5s; the room temperature anti-oxidation treatment solution is composed of: deionized water as solvent, containing 2g / L potassium dichromate;

[0051] S4: spraying the pretreated copper foil with a silane treatment solution, and drying the pretreated copper foil to obtain a low-profile roughened copper foil for a circuit board;

[0052] Deionized water was used as solvent, and the silane treatment solution contained 0.8 g / L of silane treatment agent; the working conditions of the drying treatment were: 160°C for 10 seconds;

[0053] The preparation of the silane treatment solution comprises the following steps:

[0054] Imidazole amidopropyl triethoxysilane, tetraethyl silicate, modified bisphenol A type polyaryletherketone, N,N-dimethylacetamide, and deionized water were mixed, ultrasonically treated at 45kHz for 20min, ammonia water was added, stirred for 1h to obtain a silane treatment agent, and deionized water was added to obtain a silane treatment solution;

[0055] The raw material composition of the silane treatment agent is: 3 parts of imidazole amidopropyl triethoxysilane, 1 part of tetraethyl silicate, 2 parts of modified bisphenol A type polyaryletherketone, 33 parts of N,N-dimethylacetamide, 3 parts of deionized water, and 0.2 parts of ammonia water;

[0056] The preparation of the imidazole amidopropyl triethoxysilane comprises the following steps:

[0057] Under nitrogen protection, 25 mmol imidazole and 25 mL tetrahydrofuran were mixed, the temperature was raised to 48°C, 25 mmol γ-isocyanate propyl triethoxysilane was added, and the mixture was stirred for 110 min. The mixture was decompressed and separated by column with acetone and petroleum ether in a volume ratio of 4:6 to obtain imidazole amide propyl triethoxysilane.

[0058] The preparation of modified bisphenol A type polyaryletherketone comprises the following steps:

[0059] 1) Under nitrogen protection, 1 mmol 2,2-bis[4-(4-aminophenoxybenzene)]hexafluoropropane, 2 mmol 4-chlorophthalic anhydride and 25 mL toluene were mixed, heated to 118°C for 250 min, heated to 143°C for 70 min, heated to 158°C for 70 min, discharged in anhydrous ethanol, washed with toluene 3 times, filtered and dried to obtain bischloroimidephenoxyhexafluoropropane;

[0060] 2) Under nitrogen protection, 3 g of bisphenol A, 0.9 g of 4,4'-difluorobenzophenone, and 1.6 g of bis(chloroimide)phenoxyhexafluoropropane were mixed, and 50 mL of sulfolane, 0.2 g of sodium carbonate, and 5 mL of p-xylene were added in sequence. The temperature was raised to 168°C and kept for 4 h, then raised to 178°C and kept for 2 h, and then raised to 218°C and kept for 3 h. The material was poured into deionized water, dried, and crushed. The material was washed with deionized water and anhydrous ethanol by boiling for 6 times in sequence, filtered, and dried to obtain a modified bisphenol A type polyaryletherketone.

[0061] Embodiment 3: A production process for a low-profile roughened copper foil for a circuit board, comprising the following steps:

[0062] S1: placing the copper foil in a pickling solution for pickling treatment to obtain a pickled copper foil;

[0063] The working conditions of pickling treatment are: temperature 30°C, time 8s; the composition of pickling solution is: deionized water as solvent, containing 150g / L sulfuric acid and 3g / L copper sulfate;

[0064] S2: preparing a roughening solution with sulfuric acid, copper sulfate, hydrochloric acid, indium sulfate, cerous sulfate, and hydroxyethyl cellulose, placing the pickled copper foil in the roughening solution, and performing two roughening treatments to obtain a roughened copper foil;

[0065] The working conditions of the roughening treatment are: current density 25A / dm 2 , temperature 30℃, time 15s; the composition of the roughening solution is: deionized water as solvent, containing 170g / L sulfuric acid, 10g / L copper sulfate, 20mg / L hydrochloric acid, 17mg / L indium sulfate, 44mg / L cerium sulfate, and 15mg / L hydroxyethyl cellulose;

[0066] S3: subjecting the roughened copper foil to curing treatment, high temperature anti-oxidation treatment, and room temperature anti-oxidation treatment to obtain a pretreated copper foil;

[0067] The working conditions of curing treatment are: 18A / dm 2 , temperature 40℃, time 8s; the composition of the solidifying liquid is: deionized water as solvent, containing 120g / L sulfuric acid and 40g / L copper sulfate;

[0068] The working conditions of high temperature anti-oxidation treatment are: current density 8A / dm 2 , temperature 40℃, time 8s; high temperature anti-oxidation treatment liquid composition: deionized water as solvent, containing potassium pyrophosphate 104g / L, zinc sulfate 3g / L, nickel sulfate 0.3g / L, pH value 9; room temperature anti-oxidation treatment working conditions: current density 8A / dm 2 , temperature 30℃, time 8s; the room temperature anti-oxidation treatment solution is composed of: deionized water as solvent, containing 2.5g / L potassium dichromate;

[0069] S4: spraying the pretreated copper foil with a silane treatment solution, and drying the pretreated copper foil to obtain a low-profile roughened copper foil for a circuit board;

[0070] Deionized water was used as solvent, and the silane treatment solution contained 1 g / L of silane treatment agent. The working conditions for the drying treatment were: 200°C for 8 seconds;

[0071] The preparation of the silane treatment solution comprises the following steps:

[0072] Imidazole amidopropyl triethoxysilane, tetraethyl silicate, modified bisphenol A type polyaryletherketone, N,N-dimethylacetamide, and deionized water were mixed, ultrasonically treated at 45kHz for 25 minutes, ammonia water was added, and stirred for 1.5 hours to obtain a silane treatment agent, and deionized water was added and mixed to obtain a silane treatment solution;

[0073] The raw material composition of the silane treatment agent is: 4 parts of imidazole amidopropyl triethoxysilane, 1.5 parts of tetraethyl silicate, 3 parts of modified bisphenol A type polyaryletherketone, 37 parts of N,N-dimethylacetamide, 4 parts of deionized water, and 0.3 parts of ammonia water;

[0074] The preparation of the imidazole amidopropyl triethoxysilane comprises the following steps:

[0075] Under nitrogen protection, 25 mmol imidazole and 25 mL tetrahydrofuran were mixed, the temperature was raised to 50°C, 25 mmol γ-isocyanate propyl triethoxysilane was added, and the mixture was stirred for 120 min. The mixture was decompressed and separated by column with acetone and petroleum ether in a volume ratio of 4:6 to obtain imidazole amide propyl triethoxysilane.

[0076] The preparation of modified bisphenol A type polyaryletherketone comprises the following steps:

[0077] 1) Under nitrogen protection, 1 mmol 2,2-bis[4-(4-aminophenoxybenzene)]hexafluoropropane, 2 mmol 4-chlorophthalic anhydride and 25 mL toluene were mixed, heated to 120°C and kept for 240 min, heated to 145°C and kept for 60 min, heated to 160°C and kept for 60 min, discharged in anhydrous ethanol, washed with toluene 3 times, filtered and dried to obtain bischloroimidephenoxyhexafluoropropane;

[0078] 2) Under nitrogen protection, 3 g of bisphenol A, 0.9 g of 4,4'-difluorobenzophenone, and 1.6 g of bis(chloroimide)phenoxyhexafluoropropane were mixed, and 50 mL of sulfolane, 0.2 g of sodium carbonate, and 5 mL of p-xylene were added in sequence. The mixture was heated to 170°C and kept for 3.5 h, then heated to 180°C and kept for 1.5 h, and then heated to 220°C and kept for 2.5 h. The mixture was poured into deionized water, dried, and crushed. The mixture was washed with deionized water and anhydrous ethanol by boiling for 7 times in sequence, filtered, and dried to obtain a modified bisphenol A type polyaryletherketone.

[0079] Embodiment 4: A production process for a low-profile roughened copper foil for a circuit board, comprising the following steps:

[0080] S1: placing the copper foil in a pickling solution for pickling treatment to obtain a pickled copper foil;

[0081] The working conditions of pickling treatment are: temperature 40°C, time 10s; the composition of pickling solution is: deionized water as solvent, containing 170g / L sulfuric acid and 5g / L copper sulfate;

[0082] S2: preparing a roughening solution with sulfuric acid, copper sulfate, hydrochloric acid, indium sulfate, cerous sulfate, and hydroxyethyl cellulose, placing the pickled copper foil in the roughening solution, and performing two roughening treatments to obtain a roughened copper foil;

[0083] The working conditions of the roughening treatment are: current density 30A / dm 2 , temperature 35℃, time 20s; the composition of the roughening solution is: deionized water as solvent, containing 180g / L sulfuric acid, 20g / L copper sulfate, 30mg / L hydrochloric acid, 30mg / L indium sulfate, 50mg / L cerium sulfate, and 20mg / L hydroxyethyl cellulose;

[0084] S3: subjecting the roughened copper foil to curing treatment, high temperature anti-oxidation treatment, and room temperature anti-oxidation treatment to obtain a pretreated copper foil;

[0085] The working conditions of curing treatment are: 20A / dm 2 , temperature 45°C, time 10s; the composition of the solidifying liquid is: deionized water as solvent, containing 140g / L sulfuric acid and 50g / L copper sulfate;

[0086] The working conditions of high temperature anti-oxidation treatment are: current density 10A / dm 2 , temperature 45℃, time 10s; high temperature anti-oxidation treatment liquid composition: deionized water as solvent, containing potassium pyrophosphate 110g / L, zinc sulfate 4.5g / L, nickel sulfate 0.5g / L, pH value 9.5; room temperature anti-oxidation treatment working conditions: current density 10A / dm 2 , temperature 35℃, time 10s; the room temperature anti-oxidation treatment solution is composed of: deionized water as solvent, containing 3g / L potassium dichromate;

[0087] S4: spraying the pretreated copper foil with a silane treatment solution, and drying the pretreated copper foil to obtain a low-profile roughened copper foil for a circuit board;

[0088] Deionized water was used as the solvent, and the silane treatment solution contained 1.5 g / L of silane treatment agent; the working conditions for the drying treatment were: 220°C for 6 seconds;

[0089] The preparation of the silane treatment solution comprises the following steps:

[0090] Imidazole amidopropyl triethoxysilane, tetraethyl silicate, modified bisphenol A type polyaryletherketone, N,N-dimethylacetamide, and deionized water were mixed, ultrasonically treated at 45kHz for 30 minutes, ammonia water was added, and stirred for 2 hours to obtain a silane treatment agent, and deionized water was added to mix to obtain a silane treatment solution;

[0091] The raw material composition of the silane treatment agent is: 6 parts of imidazole amidopropyl triethoxysilane, 2 parts of tetraethyl silicate, 4 parts of modified bisphenol A type polyaryletherketone, 44 parts of N,N-dimethylacetamide, 5 parts of deionized water, and 0.5 parts of ammonia water;

[0092] The preparation of the imidazole amidopropyl triethoxysilane comprises the following steps:

[0093] Under nitrogen protection, 25 mmol imidazole and 25 mL tetrahydrofuran were mixed, the temperature was raised to 52°C, 25 mmol γ-isocyanate propyl triethoxysilane was added, and the mixture was stirred for 130 min. The mixture was decompressed and separated by column with acetone and petroleum ether in a volume ratio of 4:6 to obtain imidazole amide propyl triethoxysilane.

[0094] The preparation of modified bisphenol A type polyaryletherketone comprises the following steps:

[0095] 1) Under nitrogen protection, 1 mmol 2,2-bis[4-(4-aminophenoxybenzene)]hexafluoropropane, 2 mmol 4-chlorophthalic anhydride and 25 mL toluene were mixed, heated to 122°C and kept for 230 min, heated to 147°C and kept for 50 min, heated to 162°C and kept for 50 min, discharged in anhydrous ethanol, washed with toluene 4 times, filtered and dried to obtain bischloroimidephenoxyhexafluoropropane;

[0096] 2) Under nitrogen protection, 3 g of bisphenol A, 0.9 g of 4,4'-difluorobenzophenone, and 1.6 g of bis(chloroimide)phenoxyhexafluoropropane were mixed, and 50 mL of sulfolane, 0.2 g of sodium carbonate, and 5 mL of p-xylene were added in sequence. The temperature was raised to 172° C. and kept for 3 h, then raised to 182° C. and kept for 1 h, and then raised to 222° C. and kept for 2 h. The material was poured into deionized water, dried, crushed, and washed with deionized water and anhydrous ethanol by boiling for 6-8 times in sequence. The material was filtered and dried to obtain a modified bisphenol A type polyaryletherketone.

[0097] Comparative Example 1: Taking Example 4 as the control group, γ-isocyanatepropyltriethoxysilane was used to replace imidazoleamidepropyltriethoxysilane, and other processes were normal.

[0098] Comparative Example 2: Example 4 was used as a control group, in which modified bisphenol A-type polyaryletherketone was not prepared, and other processes were normal.

[0099] The thickness of the copper foil in the embodiment and the comparative example is 35 μm.

[0100] Sources of raw materials used (for demonstration purposes only):

[0101] Indium sulfate I431960, cerium sulfate C465798, hydroxyethyl cellulose H434474, potassium pyrophosphate P100385, potassium dichromate P397531, tetraethyl silicate T110596, N,N-dimethylacetamide D108096, imidazole I108707, tetrahydrofuran T103263, γ-isocyanatepropyltriethoxysilane T106834, 2,2-dimethoxysilane [4-(4-Aminophenoxybenzene)]hexafluoropropane H102221, 4-chlorophthalic anhydride C153925, bisphenol AB108651, 4,4'-difluorobenzophenone M106424, sulfolane S110941: Aladdin reagent; sulfuric acid, copper sulfate, hydrochloric acid, zinc sulfate, nickel sulfate, ammonia water, acetone, petroleum ether, toluene, ethanol, sodium carbonate, p-xylene, analytical grade: Sinopharm Group reagent.

[0102] Performance test: The copper foils prepared in the embodiments and comparative examples were tested:

[0103] Peel strength test: Cut the copper foil with length of 50 and width of 70, take two 1080 type prepregs of the same size, place the prepregs on both sides of the substrate (copper plate), place the roughened copper foil on the prepregs, and then place an untreated copper foil on each side, press them together, then remove the untreated copper foil, make a 3mm test strip after dry film, exposure, development, and etching, turn on the peel strength tester, start measuring at a speed of 730RPM, and the interval time is 0.05s; High temperature resistance: Place the copper foil at 2 Keep the copper foil at 90℃ for 1h, observe whether it changes color, if there is no color change, it is excellent, otherwise, keep the copper foil at 260℃ for 1h, observe whether it changes color, if there is no color change, it is excellent, otherwise, keep the copper foil at 200℃ for 1h, observe whether it changes color, if there is no color change, it is qualified, otherwise it is unqualified; Corrosion resistance: put the copper foil in a sodium chloride solution with a mass concentration of 10%, keep it at 100℃ for 72h, observe whether there is any color change, corrosion and other phenomena, if there is no phenomenon, it is qualified; the results are shown in Table 1;

[0104] Table 1

[0105]

[0106] The present invention provides a low-profile roughened copper foil for a circuit board and application thereof. Through composition and process design, a low-profile roughened copper foil with corrosion resistance, high temperature resistance, water resistance and high peeling strength is prepared to meet the requirements of high-frequency and high-speed circuit boards.

[0107] By comparing Example 4 with Comparative Example 1, it can be seen that imidazoleamide propyl triethoxysilane is synthesized using imidazole and γ-isocyanate propyl triethoxysilane as raw materials, and imidazole is hybridized and introduced into the silane coupling agent as a corrosion inhibitor, thereby further improving the corrosion resistance of the copper foil and making the formed film more compact and smooth.

[0108] By comparing Example 4 with Comparative Example 2, it can be seen that the modified bisphenol A type polyaryletherketone is first synthesized with 2,2-bis[4-(4-aminophenoxybenzene)]hexafluoropropane and 4-chlorophthalic anhydride as raw materials to synthesize a monomer containing an imidophenoxyhexafluoropropane structure, and then copolymerized with bisphenol A and 4,4'-difluorobenzophenone, and an imidophenoxyhexafluoropropane group is introduced into the main chain structure of the polyetheretherketone, thereby further enhancing the heat resistance and water resistance of the polyaryletherketone, thereby improving the corrosion resistance, high temperature resistance, water resistance, peel strength and other properties of the roughened copper foil, so that it meets the requirements of high-frequency and high-speed circuit boards.

[0109] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the equivalent elements of the claims be included in the invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A production process for low-profile roughened copper foil for circuit boards, characterized in that: The following steps are involved: S1: placing the copper foil in a pickling solution for pickling treatment to obtain a pickled copper foil; S2: preparing a roughening solution with sulfuric acid, copper sulfate, hydrochloric acid, indium sulfate, cerous sulfate, and hydroxyethyl cellulose, placing the pickled copper foil in the roughening solution, and performing two roughening treatments to obtain a roughened copper foil; S3: subjecting the roughened copper foil to curing treatment, high temperature anti-oxidation treatment, and room temperature anti-oxidation treatment to obtain a pretreated copper foil; S4: spraying the pretreated copper foil with a silane treatment solution, and drying the pretreated copper foil to obtain a low-profile roughened copper foil for a circuit board.

2. A process for producing a low-profile roughened copper foil for a circuit board according to claim 1, characterized in that: The working conditions of pickling treatment are: temperature 25-40℃, time 5-10s; the composition of pickling solution is: deionized water as solvent, containing 100-170g / L sulfuric acid and 2-5g / L copper sulfate; the working conditions of curing treatment are: current density 15-20A / dm 2 , temperature 35-45°C, time 5-10s; the composition of the solidifying liquid is: deionized water as solvent, containing 80-140g / L sulfuric acid and 35-50g / L copper sulfate.

3. The production process of a low-profile roughened copper foil for a circuit board according to claim 1, characterized in that: The working conditions of the roughening treatment are: current density 20-30A / dm 2 , temperature 25-35℃, time 10-20s; the composition of the roughening solution is: deionized water as solvent, containing 160-180g / L sulfuric acid, 8-20g / L copper sulfate, 15-30mg / L hydrochloric acid, 10-30mg / L indium sulfate, 20-50mg / L cerium sulfate, and 10-20mg / L hydroxyethyl cellulose.

4. The production process of a low-profile roughened copper foil for a circuit board according to claim 1, characterized in that: The working conditions of high temperature anti-oxidation treatment are: current density 5-10A / dm 2 , temperature 35-45℃, time 5-10s; high temperature anti-oxidation treatment liquid composition: deionized water as solvent, containing potassium pyrophosphate 85-110g / L, zinc sulfate 2.5-4.5g / L, nickel sulfate 0.1-0.5g / L, pH value 8.5-9.5; room temperature anti-oxidation treatment working conditions: current density 5-10A / dm 2 , temperature 25-35℃, time 5-10s; the composition of the room temperature anti-oxidation treatment liquid is: deionized water as solvent, containing 2-3g / L potassium dichromate.

5. The production process of a low-profile roughened copper foil for a circuit board according to claim 1, characterized in that: The preparation of the silane treatment solution comprises the following steps: Imidazole amidopropyl triethoxysilane, tetraethyl silicate, modified bisphenol A type polyaryletherketone, N,N-dimethylacetamide and deionized water are mixed, ultrasonically treated at 45kHz for 20-30min, ammonia water is added, stirred for 1-2h to obtain a silane treatment agent, and deionized water is added to mix to obtain a silane treatment solution.

6. A process for producing a low-profile roughened copper foil for a circuit board according to claim 5, characterized in that: Deionized water is used as a solvent, and the silane treatment liquid contains 0.8-1.5 g / L of a silane treatment agent. The raw material composition of the silane treatment agent is as follows, by mass: 3-6 parts of imidazole amide propyl triethoxysilane, 1-2 parts of tetraethyl silicate, 2-4 parts of modified bisphenol A type polyaryletherketone, 33-44 parts of N,N-dimethylacetamide, 3-5 parts of deionized water, and 0.2-0.5 parts of ammonia water.

7. The process for producing a low-profile roughened copper foil for a circuit board according to claim 5, characterized in that: The preparation of the imidazole amidopropyl triethoxysilane comprises the following steps: Under nitrogen protection, imidazole and tetrahydrofuran were mixed, the temperature was raised to 48-52°C, γ-isocyanatepropyltriethoxysilane was added, stirred for 110-130 minutes, reduced pressure, and separated by column with acetone and petroleum ether in a volume ratio of 4:6 to obtain imidazoleamidopropyltriethoxysilane.

8. The process for producing a low-profile roughened copper foil for a circuit board according to claim 5, characterized in that: The preparation of the modified bisphenol A type polyaryletherketone comprises the following steps: 1) Under nitrogen protection, 2,2-bis[4-(4-aminophenoxybenzene)]hexafluoropropane, 4-chlorophthalic anhydride and toluene are mixed, heated to 118-122°C and kept for 230-250 min, heated to 143-147°C and kept for 50-70 min, heated to 158-162°C and kept for 50-70 min, discharged in anhydrous ethanol, washed with toluene 3-4 times, filtered and dried to obtain bischloroimidephenoxyhexafluoropropane; 2) Under nitrogen protection, bisphenol A, 4,4'-difluorobenzophenone and bis(chloroimide)phenoxyhexafluoropropane are mixed, sulfolane, sodium carbonate and p-xylene are added in sequence, the temperature is raised to 168-172°C and kept for 3-4 hours, the temperature is raised to 178-182°C and kept for 1-2 hours, the temperature is raised to 218-222°C and kept for 2-3 hours, the material is poured into deionized water, dried and crushed, washed with deionized water and anhydrous ethanol by boiling for 6-8 times in sequence, filtered and dried to obtain modified bisphenol A type polyaryletherketone.

9. A low profile roughened copper foil for a circuit board, characterized in that: The product is produced by the production process described in any one of claims 1 to 8.

10. An application of low-profile roughened copper foil for circuit boards, characterized in that: The copper foil described in claim 9 is applied to a circuit board.

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