Acidic bright copper plating agent and preparation method thereof

Abstract

The invention relates to an acidic bright copper plating agent, comprising the following raw materials by weight: 35-45 parts of copper sulfate pentahydrate, 8-12 parts of ethylenediaminetetraacetic acid, 3-6 parts of bipyridine, 3-5 parts of sodium dodecylbenzene sulfonate, 5-8 parts of sulfuric acid, 1-2 parts of polyethylene glycol, and 30-40 parts of water. The acidic bright copper plating agent of the invention adopts copper sulfate pentahydrate, ethylenediaminetetraacetic acid, bipyridine, sulfuric acid, and polyethylene glycol as a matrix material, and a continuous regulator based on modified nano-mica powder and a graphene regulator are added to coordinate and cooperate with each other to enhance the efficiency. The obtained copper plating agent optimizes the bonding strength performance and brightness of the product, and at the same time, the salt and alkali resistance stability of the product and the elongation performance of the plated product have remarkable effects.

Description

Technical Field

[0001] The invention relates to the technical field of copper plating agents, and in particular to an acid bright copper plating agent and a preparation method thereof. Background Art

[0002] Plating technology has been widely used in various fields, from daily necessities to high-tech products. The objects of plating also include various materials such as metals and plastics. Chemical copper plating is a process in circuit board manufacturing, usually also called copper plating or pore plating, which is a self-catalytic redox reaction.

[0003] Existing copper plating agents mostly use copper salts in combination with complexing agents and other raw materials. The raw materials used are relatively simple, which easily leads to poor brightness and bonding strength of the coating. At the same time, the formed coating has poor salt and alkali resistance and low elongation performance of the coating product, which limits the use efficiency of the product. Summary of the invention

[0004] In view of the defects of the prior art, the object of the present invention is to provide an acid bright copper plating agent and a preparation method thereof to solve the problems raised in the above background technology.

[0005] The present invention solves the technical problem by adopting the following technical solution:

[0006] The present invention provides an acid bright copper plating agent, comprising the following raw materials in parts by weight:

[0007] 35-45 parts of copper sulfate pentahydrate, 8-12 parts of ethylenediaminetetraacetic acid, 3-6 parts of bipyridyl, 3-5 parts of sodium dodecylbenzene sulfonate, 5-8 parts of sulfuric acid, 1-2 parts of polyethylene glycol, and 30-40 parts of water.

[0008] Preferably, the bright copper plating agent further comprises the following raw materials in parts by weight:

[0009] 40 parts of copper sulfate pentahydrate, 10 parts of ethylenediaminetetraacetic acid, 4.5 parts of bipyridyl, 4 parts of sodium dodecylbenzene sulfonate, 6.5 parts of sulfuric acid, 1.5 parts of polyethylene glycol, and 35 parts of water.

[0010] Preferably, the mass concentration of the copper sulfate pentahydrate is 10-15 g / L.

[0011] Preferably, the acidic bright copper plating agent further comprises 4 to 7 parts of a continuous regulator based on modification of nano-mica powder and 3 to 5 parts of a graphene regulator.

[0012] Preferably, the preparation method of the continuous conditioning agent modified by nano-mica powder is:

[0013] S01: placing the nano-mica powder in a sufficient amount of 5% by mass potassium permanganate solution, stirring and mixing, then washing, drying, and then performing thermal efficiency improvement treatment to obtain a thermally efficient nano-mica agent;

[0014] The specific steps of thermal efficiency improvement treatment are as follows:

[0015] First, heat to 210-230°C at a rate of 2-5°C / min, keep warm for 10-15min, then heat to 330-340°C at a rate of 1-3°C / min, keep warm for 5-10min, and finally air cool to room temperature;

[0016] S02: Blend and stir 4-6 parts of thermally effective nano-mica agent, 2-5 parts of sodium lignin sulfonate solution, 5-7 parts of chitosan solution and 1-2 parts of stearic acid at a stirring speed of 550-650 r / min for 20-30 min. After stirring, wash with water and dry to obtain a pre-adjusted nano-mica agent;

[0017] S03: The pre-adjusted nano-mica agent and sodium alginate continuous adjusting agent are subjected to ball milling modification treatment at a weight ratio of 5:3, the ball milling speed is 1000-1500r / min, the ball milling time is 1-2h, and after the ball milling is completed, the continuous adjusting agent is washed with water and dried to obtain a continuous adjusting agent modified based on nano-mica powder.

[0018] Preferably, the mass fraction of the sodium lignin sulfonate solution is 10-15%; the mass fraction of the chitosan solution is 2-5%.

[0019] Preferably, the preparation method of the sodium alginate continuous conditioning agent is:

[0020] Add 3-6 parts of sodium alginate and 1-3 parts of silane coupling agent KH560 to 7-11 parts of yttrium nitrate solution, stir at a speed of 350-450 r / min for 20-30 minutes, then add 2-4 parts of nano-silicon dioxide and 1-3 parts of phosphate buffer solution, and stir at a speed of 750-850 r / min for 10-20 minutes to obtain a sodium alginate continuous adjuster.

[0021] Preferably, the pH value of the phosphate buffer solution is 5.5; and the mass fraction of the yttrium nitrate solution is 3-5%.

[0022] Preferably, the preparation method of the graphene regulator is:

[0023] S101: irradiating the graphene in a proton irradiation box for 10 to 15 minutes at an irradiation power of 350 to 400 W, and obtaining a graphene irradiation agent after the irradiation is completed;

[0024] S102: 4 to 7 parts of graphene irradiating agent, 3 to 6 parts of 5% by mass lanthanum chloride solution, 1 to 2 parts of carboxymethyl cellulose, and 0.25 to 0.35 parts of nano-silica sol are mixed and ball-milled, and after the ball-milling is completed, the mixture is washed with water and dried to obtain a graphene conditioning agent.

[0025] Preferably, the ball milling speed of the blending ball milling treatment is 1100-1200 r / min, and the ball milling time is 1-2 h.

[0026] The present invention also provides a method for preparing an acid bright copper plating agent, comprising the following steps:

[0027] Copper sulfate pentahydrate, sulfuric acid and water are mixed in the first stage, and then a continuous regulator based on nano-mica powder modification, a graphene regulator and sodium dodecylbenzene sulfonate are added and mixed in the second stage, and finally ethylenediaminetetraacetic acid, bipyridine and polyethylene glycol are added and mixed in the third stage. After the mixing is completed, the acidic bright copper plating agent of the present invention is obtained.

[0028] Preferably, the speed of the first-stage mixing is 450-550 r / min, and the first-stage mixing time is 20-30 min; the speed of the second-stage mixing is 750-850 r / min, and the second-stage mixing time is 10-20 min; the speed of the third-stage mixing is 350-450 r / min, and the second-stage mixing time is 35-40 min.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] 1. The acidic bright copper plating agent of the present invention adopts copper sulfate pentahydrate, ethylenediaminetetraacetic acid, bipyridine, sulfuric acid and polyethylene glycol as the base material, and adds a continuous regulator based on nano-mica powder modification and a graphene regulator to coordinate and cooperate with each other to enhance the efficiency. The copper plating agent obtained optimizes the bonding strength performance and brightness of the product, and at the same time, the salt and alkali resistance stability of the product and the elongation performance of the coating product have significant effects;

[0031] 2. The continuous conditioning agent modified by nano-mica powder adopts nano-mica powder to be treated with potassium permanganate solution to optimize its active efficiency, and then improves the thermal efficiency by heating to 210-230°C at a rate of 2-5°C / min, keeping warm for 10-15min, and then heating to 330-340°C at a rate of 1-3°C / min, keeping warm for 5-10min, and finally air-cooling to room temperature. The interlayer spacing of nano-mica is optimized by a staged heating treatment, and the interlayer spacing tolerance is improved, so as to better combine the interface between the raw materials in the system and improve the performance of the product. The nano-mica powder is improved by mixing and stirring the sodium lignin sulfonate solution, the chitosan solution and the stearic acid, and the active efficiency of the nano-mica powder is optimized, so as to better cooperate with the sodium alginate continuous conditioning agent and improve the performance of the product.

[0032] 3. Sodium alginate continuous adjuster is made by coordinating sodium alginate, silane coupling agent KH560 and yttrium nitrate solution, and then blended with nano silicon dioxide and phosphate buffer solution. Through the coordination between the raw materials, and the use of nano silicon dioxide with high specific surface area and sodium alginate continuous adjuster raw materials, synergistic nano mica powder is prepared together to enhance the product's bonding strength and brightness, salt and alkali resistance stability, and elongation performance of the coating product;

[0033] 4. The graphene regulator uses graphene that has been irradiated with protons to optimize its active performance, and then it is blended and ball-milled with lanthanum chloride solution, carboxymethyl cellulose, and nano-silica sol to enhance the product performance by distributing graphene in a flaky system. At the same time, nano-mica powder is co-mixed to enhance the distribution of graphene through the interlayer spacing accommodation of the nano-mica powder. The synergistic effect of the improved and optimized graphene regulator and the continuous regulator modified based on nano-mica powder is enhanced, and the performance of the product is further improved. DETAILED DESCRIPTION

[0034] The following is a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with specific embodiments. 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.

[0035] An acid bright copper plating agent of this embodiment includes the following raw materials in parts by weight:

[0036] 35-45 parts of copper sulfate pentahydrate, 8-12 parts of ethylenediaminetetraacetic acid, 3-6 parts of bipyridyl, 3-5 parts of sodium dodecylbenzene sulfonate, 5-8 parts of sulfuric acid, 1-2 parts of polyethylene glycol, and 30-40 parts of water.

[0037] The bright copper plating agent of this embodiment also includes the following raw materials in parts by weight:

[0038] 40 parts of copper sulfate pentahydrate, 10 parts of ethylenediaminetetraacetic acid, 4.5 parts of bipyridyl, 4 parts of sodium dodecylbenzene sulfonate, 6.5 parts of sulfuric acid, 1.5 parts of polyethylene glycol, and 35 parts of water.

[0039] The mass concentration of copper sulfate pentahydrate in this embodiment is 10-15 g / L.

[0040] The acid bright copper plating agent of this embodiment further includes 4 to 7 parts of continuous adjusting agent modified based on nano-mica powder and 3 to 5 parts of graphene adjusting agent.

[0041] Preferably, the preparation method of the continuous conditioning agent modified by nano-mica powder is:

[0042] S01: placing the nano-mica powder in a sufficient amount of 5% by mass potassium permanganate solution, stirring and mixing, then washing, drying, and then performing thermal efficiency improvement treatment to obtain a thermally efficient nano-mica agent;

[0043] The specific steps of thermal efficiency improvement treatment are as follows:

[0044] First, heat to 210-230°C at a rate of 2-5°C / min, keep warm for 10-15min, then heat to 330-340°C at a rate of 1-3°C / min, keep warm for 5-10min, and finally air cool to room temperature;

[0045] S02: Blend and stir 4-6 parts of thermally effective nano-mica agent, 2-5 parts of sodium lignin sulfonate solution, 5-7 parts of chitosan solution and 1-2 parts of stearic acid at a stirring speed of 550-650 r / min for 20-30 min. After stirring, wash with water and dry to obtain a pre-adjusted nano-mica agent;

[0046] S03; the pre-adjusted nano-mica agent and sodium alginate continuous adjustment agent are ball-milled at a weight ratio of 5:3, the ball milling speed is 1000-1500r / min, the ball milling time is 1-2h, and after the ball milling is completed, the mixture is washed with water and dried to obtain a continuous adjustment agent modified based on nano-mica powder.

[0047] The mass fraction of the sodium lignin sulfonate solution in this embodiment is 10-15%; the mass fraction of the chitosan solution is 2-5%.

[0048] The preparation method of the sodium alginate continuous conditioning agent of this embodiment is:

[0049] Add 3-6 parts of sodium alginate and 1-3 parts of silane coupling agent KH560 to 7-11 parts of yttrium nitrate solution, stir at a speed of 350-450 r / min for 20-30 minutes, then add 2-4 parts of nano-silicon dioxide and 1-3 parts of phosphate buffer solution, and stir at a speed of 750-850 r / min for 10-20 minutes to obtain a sodium alginate continuous adjuster.

[0050] The pH value of the phosphate buffer solution in this embodiment is 5.5; the mass fraction of the yttrium nitrate solution is 3-5%.

[0051] The preparation method of the graphene regulator of this embodiment is:

[0052] S101: irradiating the graphene in a proton irradiation box for 10 to 15 minutes at an irradiation power of 350 to 400 W, and obtaining a graphene irradiation agent after the irradiation is completed;

[0053] S102: 4 to 7 parts of graphene irradiating agent, 3 to 6 parts of 5% by mass lanthanum chloride solution, 1 to 2 parts of carboxymethyl cellulose, and 0.25 to 0.35 parts of nano-silica sol are mixed and ball-milled, and after the ball-milling is completed, the mixture is washed with water and dried to obtain a graphene conditioning agent.

[0054] The ball milling speed of the blended ball milling treatment in this embodiment is 1100-1200 r / min, and the ball milling is 1-2 hours.

[0055] A method for preparing an acid bright copper plating agent in this embodiment comprises the following steps:

[0056] Copper sulfate pentahydrate, sulfuric acid and water are mixed in the first stage, and then a continuous regulator based on nano-mica powder modification, a graphene regulator and sodium dodecylbenzene sulfonate are added and mixed in the second stage, and finally ethylenediaminetetraacetic acid, bipyridine and polyethylene glycol are added and mixed in the third stage. After the mixing is completed, the acidic bright copper plating agent of the present invention is obtained.

[0057] The speed of the first-stage mixing in this embodiment is 450-550r / min, and the first-stage mixing time is 20-30min; the speed of the second-stage mixing is 750-850r / min, and the second-stage mixing time is 10-20min; the speed of the third-stage mixing is 350-450r / min, and the second-stage mixing time is 35-40min.

[0058] Example 1.

[0059] An acid bright copper plating agent of this embodiment includes the following raw materials in parts by weight:

[0060] 35 parts of copper sulfate pentahydrate, 8 parts of ethylenediaminetetraacetic acid, 3 parts of bipyridine, 3 parts of sodium dodecylbenzene sulfonate, 5 parts of sulfuric acid, 1 part of polyethylene glycol, and 30-40 parts of water.

[0061] The mass concentration of copper sulfate pentahydrate in this embodiment is 10g / L.

[0062] The acid bright copper plating agent of this embodiment also includes 4 parts of continuous regulator based on modification of nano-mica powder and 3 parts of graphene regulator.

[0063] The preparation method of the continuous conditioning agent modified by nano-mica powder in this embodiment is:

[0064] S01: placing the nano-mica powder in a sufficient amount of 5% by mass potassium permanganate solution, stirring and mixing, then washing, drying, and then performing thermal efficiency improvement treatment to obtain a thermally efficient nano-mica agent;

[0065] The specific steps of thermal efficiency improvement treatment are as follows:

[0066] First, heat to 210°C at a rate of 2°C / min, keep warm for 10 min, then heat to 330°C at a rate of 1°C / min, keep warm for 5 min, and finally air cool to room temperature;

[0067] S02: Blend and stir 4 parts of thermal-effective nano-mica agent, 2 parts of sodium lignin sulfonate solution, 5 parts of chitosan solution and 1 part of stearic acid at a stirring speed of 550 r / min for 20 min. After stirring, wash with water and dry to obtain a pre-adjusted nano-mica agent;

[0068] S03: The pre-adjusted nano-mica agent and sodium alginate continuous adjusting agent are subjected to ball milling modification treatment at a weight ratio of 5:3. The ball milling speed is 1000r / min and the ball milling time is 1h. After the ball milling is completed, the continuous adjusting agent is washed with water and dried to obtain a continuous adjusting agent modified based on nano-mica powder.

[0069] The mass fraction of the sodium lignin sulfonate solution in this embodiment is 10%; the mass fraction of the chitosan solution is 2%.

[0070] The preparation method of the sodium alginate continuous conditioning agent of this embodiment is:

[0071] Add 3 parts of sodium alginate and 1 part of silane coupling agent KH560 to 7 parts of yttrium nitrate solution, stir at 350 r / min for 20 minutes, then add 2 parts of nano-silicon dioxide and 1 part of phosphate buffer solution, and stir at 750 r / min for 10 minutes to obtain a sodium alginate continuous adjuster.

[0072] The pH value of the phosphate buffer solution in this embodiment is 5.5; the mass fraction of the yttrium nitrate solution is 3%.

[0073] The preparation method of the graphene regulator of this embodiment is:

[0074] S101: irradiating the graphene in a proton irradiation box for 10 minutes at an irradiation power of 350 W, and obtaining a graphene irradiation agent after the irradiation is completed;

[0075] S102: 4 parts of graphene irradiating agent, 3 parts of 5% by mass lanthanum chloride solution, 1 part of carboxymethyl cellulose and 0.25 parts of nano-silica sol are mixed and ball-milled, and after the ball-milling is completed, the mixture is washed with water and dried to obtain a graphene conditioning agent.

[0076] The ball milling speed of the blended ball milling treatment in this embodiment is 1100 r / min, and the ball milling is 1 hour.

[0077] A method for preparing an acid bright copper plating agent in this embodiment comprises the following steps:

[0078] Copper sulfate pentahydrate, sulfuric acid and water are mixed in the first stage, and then a continuous regulator based on nano-mica powder modification, a graphene regulator and sodium dodecylbenzene sulfonate are added and mixed in the second stage, and finally ethylenediaminetetraacetic acid, bipyridine and polyethylene glycol are added and mixed in the third stage. After the mixing is completed, the acidic bright copper plating agent of the present invention is obtained.

[0079] In this embodiment, the speed of the first-stage mixing is 450r / min, and the first-stage mixing time is 20min; the speed of the second-stage mixing is 750r / min, and the second-stage mixing time is 10min; the speed of the third-stage mixing is 350r / min, and the second-stage mixing time is 35min.

[0080] Example 2.

[0081] An acid bright copper plating agent of this embodiment includes the following raw materials in parts by weight:

[0082] 45 parts of copper sulfate pentahydrate, 12 parts of ethylenediaminetetraacetic acid, 6 parts of bipyridyl, 5 parts of sodium dodecylbenzene sulfonate, 8 parts of sulfuric acid, 2 parts of polyethylene glycol, and 40 parts of water.

[0083] The mass concentration of copper sulfate pentahydrate in this embodiment is 15g / L.

[0084] The acid bright copper plating agent of this embodiment also includes 7 parts of continuous regulator based on modification of nano-mica powder and 5 parts of graphene regulator.

[0085] The preparation method of the continuous conditioning agent modified by nano-mica powder in this embodiment is:

[0086] S01: placing the nano-mica powder in a sufficient amount of 5% by mass potassium permanganate solution, stirring and mixing, then washing, drying, and then performing thermal efficiency improvement treatment to obtain a thermally efficient nano-mica agent;

[0087] The specific steps of thermal efficiency improvement treatment are as follows:

[0088] First, heat to 230°C at a rate of 5°C / min, keep warm for 15 min, then heat to 340°C at a rate of 3°C / min, keep warm for 10 min, and finally air cool to room temperature;

[0089] S02: 6 parts of thermal nano-mica agent, 5 parts of sodium lignin sulfonate solution, 7 parts of chitosan solution and 2 parts of stearic acid are mixed and stirred at a stirring speed of 650 r / min for 30 min. After the stirring is completed, the mixture is washed with water and dried to obtain a pre-adjusted nano-mica agent;

[0090] S03: The pre-adjusted nano-mica agent and sodium alginate continuous adjusting agent are subjected to ball milling modification treatment at a weight ratio of 5:3. The ball milling speed is 1500r / min and the ball milling time is 2h. After the ball milling is completed, the continuous adjusting agent is washed with water and dried to obtain a continuous adjusting agent modified based on nano-mica powder.

[0091] The mass fraction of the sodium lignin sulfonate solution in this embodiment is 15%; the mass fraction of the chitosan solution is 5%.

[0092] The preparation method of the sodium alginate continuous conditioning agent of this embodiment is:

[0093] 6 parts of sodium alginate and 3 parts of silane coupling agent KH560 were added to 11 parts of yttrium nitrate solution, first stirred at a speed of 450 r / min for 30 minutes, and then 4 parts of nano-silicon dioxide and 3 parts of phosphate buffer solution were added, and then stirred at a speed of 850 r / min for 20 minutes to obtain a sodium alginate continuous adjuster.

[0094] The pH value of the phosphate buffer solution in this embodiment is 5.5; the mass fraction of the yttrium nitrate solution is 5%.

[0095] The preparation method of the graphene regulator of this embodiment is:

[0096] S101: irradiating the graphene in a proton irradiation box for 15 minutes at an irradiation power of 400 W, and obtaining a graphene irradiation agent after the irradiation is completed;

[0097] S102: 7 parts of graphene irradiating agent, 6 parts of 5% by mass lanthanum chloride solution, 2 parts of carboxymethyl cellulose and 0.35 parts of nano-silica sol are mixed and ball-milled. After the ball-milling is completed, the mixture is washed with water and dried to obtain a graphene conditioning agent.

[0098] The ball milling speed of the blended ball milling treatment in this embodiment is 1200 r / min, and the ball milling is 2 h.

[0099] A method for preparing an acid bright copper plating agent in this embodiment comprises the following steps:

[0100] Copper sulfate pentahydrate, sulfuric acid and water are mixed in the first stage, and then a continuous regulator based on nano-mica powder modification, a graphene regulator and sodium dodecylbenzene sulfonate are added and mixed in the second stage, and finally ethylenediaminetetraacetic acid, bipyridine and polyethylene glycol are added and mixed in the third stage. After the mixing is completed, the acidic bright copper plating agent of the present invention is obtained.

[0101] In this embodiment, the speed of the first-stage mixing is 550r / min, and the first-stage mixing time is 30min; the speed of the second-stage mixing is 850r / min, and the second-stage mixing time is 20min; the speed of the third-stage mixing is 450r / min, and the second-stage mixing time is 40min.

[0102] Example 3.

[0103] An acid bright copper plating agent of this embodiment includes the following raw materials in parts by weight:

[0104] 40 parts of copper sulfate pentahydrate, 10 parts of ethylenediaminetetraacetic acid, 4.5 parts of bipyridyl, 4 parts of sodium dodecylbenzene sulfonate, 6.5 parts of sulfuric acid, 1.5 parts of polyethylene glycol, and 35 parts of water.

[0105] The mass concentration of copper sulfate pentahydrate in this embodiment is 12.5 g / L.

[0106] The acid bright copper plating agent of this embodiment also includes 5.5 parts of continuous regulator based on nano-mica powder modification and 4 parts of graphene regulator.

[0107] The preparation method of the continuous conditioning agent modified by nano-mica powder in this embodiment is:

[0108] S01: placing the nano-mica powder in a sufficient amount of 5% by mass potassium permanganate solution, stirring and mixing, then washing, drying, and then performing thermal efficiency improvement treatment to obtain a thermally efficient nano-mica agent;

[0109] The specific steps of thermal efficiency improvement treatment are as follows:

[0110] First, the temperature was raised to 220°C at a rate of 3.5°C / min, kept at that temperature for 12.5min, then raised to 335°C at a rate of 2°C / min, kept at that temperature for 7.5min, and finally air-cooled to room temperature;

[0111] S02: 5 parts of thermally effective nano mica agent, 3.5 parts of sodium lignin sulfonate solution, 6 parts of chitosan solution and 1.5 parts of stearic acid are mixed and stirred at a stirring speed of 600 r / min for 25 min. After the stirring is completed, the mixture is washed with water and dried to obtain a pre-adjusted nano mica agent;

[0112] S03: The pre-adjusted nano-mica agent and sodium alginate continuous adjusting agent are subjected to ball milling modification treatment at a weight ratio of 5:3, the ball milling speed is 1250r / min, the ball milling time is 1.5h, and after the ball milling is completed, the continuous adjusting agent is washed with water and dried to obtain a continuous adjusting agent modified based on nano-mica powder.

[0113] The mass fraction of the sodium lignin sulfonate solution in this embodiment is 15%; the mass fraction of the chitosan solution is 3.5%.

[0114] The preparation method of the sodium alginate continuous conditioning agent of this embodiment is:

[0115] 4.5 parts of sodium alginate and 2 parts of silane coupling agent KH560 were added to 8 parts of yttrium nitrate solution, first stirred at a speed of 400 r / min for 25 minutes, and then 3 parts of nano-silicon dioxide and 2 parts of phosphate buffer solution were added, and then stirred at a speed of 800 r / min for 15 minutes to obtain a sodium alginate continuous adjuster.

[0116] The pH value of the phosphate buffer solution in this embodiment is 5.5; the mass fraction of the yttrium nitrate solution is 3-5%.

[0117] The preparation method of the graphene regulator of this embodiment is:

[0118] S101: irradiating the graphene in a proton irradiation box for 12 minutes at an irradiation power of 370 W, and obtaining a graphene irradiation agent after the irradiation is completed;

[0119] S102: 5.5 parts of graphene irradiating agent, 4.5 parts of 5% by mass lanthanum chloride solution, 1.5 parts of carboxymethyl cellulose and 0.30 parts of nano-silica sol are mixed and ball-milled, and after the ball-milling is completed, the mixture is washed with water and dried to obtain a graphene conditioning agent.

[0120] The ball milling speed of the blended ball milling treatment in this embodiment is 1150 r / min, and the ball milling is 1.5 h.

[0121] A method for preparing an acid bright copper plating agent in this embodiment comprises the following steps:

[0122] Copper sulfate pentahydrate, sulfuric acid and water are mixed in the first stage, and then a continuous regulator based on nano-mica powder modification, a graphene regulator and sodium dodecylbenzene sulfonate are added and mixed in the second stage, and finally ethylenediaminetetraacetic acid, bipyridine and polyethylene glycol are added and mixed in the third stage. After the mixing is completed, the acidic bright copper plating agent of the present invention is obtained.

[0123] In this embodiment, the speed of the first-stage mixing is 500r / min, and the first-stage mixing time is 25min; the speed of the second-stage mixing is 800r / min, and the second-stage mixing time is 15min; the speed of the third-stage mixing is 400r / min, and the second-stage mixing time is 37min.

[0124] Comparative Example 1.

[0125] The difference from Example 3 is that the continuous conditioning agent modified by nano-mica powder is not added.

[0126] Comparative Example 2.

[0127] The difference from Example 3 is that no thermal efficiency improvement treatment is used in the preparation of the continuous conditioning agent modified based on nano-mica powder.

[0128] Comparative Example 3.

[0129] The difference from Example 3 is that the S02 step is not used in the preparation of the continuous conditioning agent modified based on nano-mica powder.

[0130] Comparative Example 4.

[0131] The difference from Example 3 is that sodium alginate and conditioning agent treatment are not used in the preparation of the nano-mica modifier.

[0132] Comparative Example 5.

[0133] The difference from Example 3 is that no graphene regulator is added.

[0134] Comparative Example 6.

[0135] The difference from Example 3 is that S102 treatment is not used in the graphene regulator.

[0136] Comparative Example 7.

[0137] The difference from Example 3 is that no nano-silica sol is added in the S102 treatment, and the lanthanum chloride solution is replaced by deionized water.

[0138] The substrate is immersed in the products of Examples 1-3 and Comparative Examples 1-7 for plating treatment to form a copper-plated layer, and the bonding strength and surface brightness of the copper-plated layer and the elongation of the plating layer are tested;

[0139] The product was placed in 5% sodium chloride salt spray for 12 hours to measure its salt spray resistance stability:

[0140] The performance measurement results are as follows

[0141]

[0142]

[0143] From Examples 1-3 and Comparative Examples 1-7, it can be concluded that

[0144] The product of Example 3 of the present invention has excellent bonding strength, brightness and elongation under normal conditions, and the product performance can be improved in a coordinated manner. At the same time, it still has excellent performance stability under salt corrosion conditions;

[0145] From Comparative Examples 1-4, Comparative Example 5 and Example 3, it can be seen that the present invention does not add one of the continuous regulator based on nano-mica powder modification and the graphene regulator, and the performance of the product deteriorates significantly. The performance effect of the product is most obvious when the two are coordinated and enhanced together.

[0146] The performance of the products tended to deteriorate when the continuous conditioning agent modified by nano-mica powder was not treated with thermal efficiency improvement, the continuous conditioning agent modified by nano-mica powder was not treated with S02 step, and the continuous conditioning agent modified by sodium alginate was not used in the preparation of the nano-mica modifier. The continuous conditioning agent modified by nano-mica powder prepared by the method of the present invention had the most significant performance effect. The effects of other methods were not as obvious as those of the present invention. The performance change trend of the products was more obvious when the continuous conditioning agent modified by sodium alginate was not used in the preparation of the nano-mica modifier.

[0147] It can be seen from Comparative Examples 6-7 and Example 3 that the graphene regulator was not treated with S102, no nano-silica sol was added in the S102 treatment, and the lanthanum chloride solution was replaced with deionized water. The performance of the products tended to deteriorate. The S102 treatment obtained by the specific method of the present invention had the most significant effect.

[0148] Based on the fact that sodium alginate and continuous conditioning treatment have a significant impact on the performance of the product, further research is conducted on this:

[0149] The preparation method of sodium alginate continuous adjuster is:

[0150] 4.5 parts of sodium alginate and 2 parts of silane coupling agent KH560 are added to 8 parts of yttrium nitrate solution, first stirred at a speed of 400 r / min for 25 minutes, then 3 parts of nano-silicon dioxide and 2 parts of phosphate buffer solution are added, and then stirred at a speed of 800 r / min for 15 minutes to obtain a sodium alginate continuous adjuster; the pH value of the phosphate buffer solution is 5.5; the mass fraction of the yttrium nitrate solution is 3-5%.

[0151] Experimental example 1.

[0152] The only difference from Example 3 is that no sodium alginate is added in the preparation of the sodium alginate continuous adjusting agent.

[0153] Experimental example 2.

[0154] The only difference from Example 3 is that no nano-silicon dioxide is added in the preparation of the sodium alginate and conditioning agent.

[0155] Experimental Example 3.

[0156] The only difference from Example 3 is that the silane coupling agent KH560 is not added in the preparation of the sodium alginate continuous adjuster.

[0157] Experimental Example 4.

[0158] The only difference from Example 3 is that deionized water is used instead of yttrium nitrate solution in the preparation of sodium alginate continuous adjuster.

[0159]

[0160]

[0161] It can be seen from Experimental Examples 1-4 that when no nano-silicon dioxide is added in the preparation of the sodium alginate continuous regulator, the performance change trend of the product is the largest, followed by the yttrium nitrate solution replaced by deionized water, and at the same time, no sodium alginate and silane coupling agent KH560 are added, and the performance of the product also shows a trend of deterioration. The sodium alginate continuous regulator obtained by the method and raw materials of the present invention has the most significant performance effect of the product. The preparation of the sodium alginate continuous regulator of the present invention is unique, and the effect of replacing it by other methods is not as obvious as that of the present invention.

[0162] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0163] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. An acid bright copper plating agent, characterized in that: It includes the following raw materials in parts by weight: 35-45 parts of copper sulfate pentahydrate, 8-12 parts of ethylenediaminetetraacetic acid, 3-6 parts of bipyridyl, 3-5 parts of sodium dodecylbenzene sulfonate, 5-8 parts of sulfuric acid, 1-2 parts of polyethylene glycol, 30-40 parts of water; The acid bright copper plating agent also includes 4 to 7 parts of continuous regulator based on nano-mica powder modification and 3 to 5 parts of graphene regulator; The preparation method of the continuous conditioning agent modified by nano-mica powder is as follows: S01: placing the nano-mica powder in a sufficient amount of 5% by mass potassium permanganate solution, stirring and mixing, then washing and drying, and then performing thermal efficiency improvement treatment to obtain a thermally efficient nano-mica agent; The specific steps of thermal efficiency improvement treatment are as follows: First, heat to 210-230°C at a rate of 2-5°C / min, keep warm for 10-15min, then heat to 330-340°C at a rate of 1-3°C / min, keep warm for 5-10min, and finally air cool to room temperature; S02: Blend and stir 4-6 parts of thermally effective nano-mica agent, 2-5 parts of sodium lignin sulfonate solution, 5-7 parts of chitosan solution and 1-2 parts of stearic acid at a stirring speed of 550-650 r / min for 20-30 min. After stirring, wash with water and dry to obtain a pre-adjusted nano-mica agent; S03: The pre-adjusted nano-mica agent and sodium alginate continuous conditioning agent are subjected to ball milling modification treatment according to a weight ratio of 5:3, the ball milling speed is 1000-1500r / min, the ball milling time is 1-2h, and after the ball milling is completed, the continuous conditioning agent is washed with water and dried to obtain a continuous conditioning agent modified with nano-mica powder; The preparation method of the sodium alginate continuous regulator is: Add 3 to 6 parts of sodium alginate and 1 to 3 parts of silane coupling agent KH560 to 7 to 11 parts of yttrium nitrate solution, stir at a speed of 350 to 450 r / min for 20 to 30 minutes, then add 2 to 4 parts of nano-silicon dioxide and 1 to 3 parts of phosphate buffer solution, and stir at a speed of 750 to 850 r / min for 10 to 20 minutes to obtain a sodium alginate continuous adjuster; The preparation method of the graphene regulator is: S101: irradiating the graphene in a proton irradiation box for 10 to 15 minutes at an irradiation power of 350 to 400 W, and obtaining a graphene irradiation agent after the irradiation is completed; S102: 4 to 7 parts of graphene irradiating agent, 3 to 6 parts of 5% by mass lanthanum chloride solution, 1 to 2 parts of carboxymethyl cellulose and 0.25 to 0.35 parts of nano-silica sol are mixed and ball-milled, and after the ball-milling is completed, the mixture is washed with water and dried to obtain a graphene conditioning agent; wherein the ball-milling speed of the mixed ball-milling treatment is 1100 to 1200 r / min, and the ball-milling is performed for 1 to 2 hours.

2. An acid bright copper plating agent according to claim 1, characterized in that: 40 parts of copper sulfate pentahydrate, 10 parts of ethylenediaminetetraacetic acid, 4.5 parts of bipyridyl, 4 parts of sodium dodecylbenzene sulfonate, 6.5 parts of sulfuric acid, 1.5 parts of polyethylene glycol, and 35 parts of water.

3. An acid bright copper plating agent according to claim 1, characterized in that: The mass concentration of the copper sulfate pentahydrate is 10-15 g / L.

4. An acid bright copper plating agent according to claim 1, characterized in that: The mass fraction of the sodium lignin sulfonate solution is 10-15%; the mass fraction of the chitosan solution is 2-5%.

5. An acid bright copper plating agent according to claim 1, characterized in that: The pH value of the phosphate buffer solution is 5.5; the mass fraction of the yttrium nitrate solution is 3-5%.

6. A method for preparing the acid bright copper plating agent according to any one of claims 1 to 5, characterized in that: The following steps are involved: Copper sulfate pentahydrate, sulfuric acid and water are mixed in the first stage, and then a continuous regulator based on nano-mica powder modification, a graphene regulator and sodium dodecylbenzene sulfonate are added and mixed in the second stage, and finally ethylenediaminetetraacetic acid, bipyridine and polyethylene glycol are added and mixed in the third stage. After the mixing is completed, an acidic bright copper plating agent is obtained.

7. The method for preparing an acid bright copper plating agent according to claim 6, characterized in that: The speed of the first-stage mixing is 450-550r / min, and the first-stage mixing time is 20-30min; the speed of the second-stage mixing is 750-850r / min, and the second-stage mixing time is 10-20min; the speed of the third-stage mixing is 350-450r / min, and the second-stage mixing time is 35-40min.

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