CN119612974A - Method for enhancing interface bonding strength of insulating substrate and metal layer - Google Patents
Method for enhancing interface bonding strength of insulating substrate and metal layer Download PDFInfo
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- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
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Abstract
本发明公开了一种增强绝缘基板与金属层界面结合强度的方法，其特征在于，包括以下步骤：A.将改性剂接枝于硅烷偶联剂，得到改性硅烷偶联剂；将改性硅烷偶联剂进行水解处理，得到改性硅烷偶联剂水解液；B.将改性硅烷偶联剂水解液与石墨烯溶液进行混合，得到改性硅烷偶联剂‑石墨烯复合液；C.将改性硅烷偶联剂‑石墨烯复合液涂覆在绝缘基板的表面，得到硅烷偶联剂‑石墨烯复合涂层，干燥处理后形成具有导电层的绝缘基板；D.对具有导电层的绝缘基板进行电镀，得到具有金属层的绝缘基板。本发明提出的一种增强绝缘基板与金属层界面结合强度的方法，通过将改性硅烷偶联剂‑石墨烯复合液涂覆在绝缘基板的表面，提升了绝缘基板与金属层的界面结合强度。The present invention discloses a method for enhancing the interfacial bonding strength between an insulating substrate and a metal layer, characterized in that the method comprises the following steps: A. grafting a modifier to a silane coupling agent to obtain a modified silane coupling agent; hydrolyzing the modified silane coupling agent to obtain a modified silane coupling agent hydrolyzate; B. mixing the modified silane coupling agent hydrolyzate with a graphene solution to obtain a modified silane coupling agent-graphene composite liquid; C. coating the modified silane coupling agent-graphene composite liquid on the surface of an insulating substrate to obtain a silane coupling agent-graphene composite coating, and forming an insulating substrate with a conductive layer after drying; D. electroplating the insulating substrate with a conductive layer to obtain an insulating substrate with a metal layer. The present invention proposes a method for enhancing the interfacial bonding strength between an insulating substrate and a metal layer, and improves the interfacial bonding strength between the insulating substrate and the metal layer by coating the modified silane coupling agent-graphene composite liquid on the surface of the insulating substrate.
Description
Technical Field
The invention relates to the technical field of electroplating, in particular to a method for enhancing the bonding strength of an insulating substrate and a metal interface.
Background
In the conventional process for constructing a metal layer on an insulating substrate, copper foil is deposited on the surface of the insulating substrate by an electroless plating method to serve as a conductive interface, and then the copper layer is thickened by an electroplating method to prepare the metal layer. Although the electroless copper plating technology is mature, the following inherent defects still exist that (1) the reducing agent used in electroless copper plating is mostly toxic formaldehyde, which causes serious pollution to the environment, (2) the complexing agent in the plating solution is complex to treat, a special vein breaking process is needed to reduce the influence on wastewater treatment, and a great challenge is brought to environmental protection, and (3) the interface bonding strength with a low-surface-energy substrate is insufficient, which may affect the overall performance of the product.
In order to overcome the above-mentioned drawbacks, researchers have innovatively proposed a direct electroplating process. The process provides a necessary conductive basis for electroplating operation by coating a layer of conductive material on the surface of the insulating substrate. The graphene is a two-dimensional carbon nanomaterial consisting of carbon atoms in sp 2 hybridized orbits, and has a hexagonal honeycomb lattice structure, so that the graphene has excellent conductive performance and mechanical strength, and provides an operation foundation for a direct electroplating technology of the graphene serving as a conductive layer. For example, chinese patent publication No. CN110351956a provides a method for directly electroplating a circuit board based on graphene film formation, which forms a conductive layer on the circuit board by a graphene film formation process, successfully replaces the conventional electroless copper plating step, and realizes direct electroplating on an insulating substrate. In addition, chinese patent publication No. CN110158132a also proposes a method for electroplating an insulating material, which also implements direct electroplating on an insulating substrate by constructing a graphite nano-sheet line on the surface of the insulating material. However, the two methods still have the problem of weak bonding force between the metal layer and the surface of the insulating material.
In order to improve the interface bonding strength between the insulating substrate and the metal layer, in the prior art, a bonding aid of an oligomer (with a molecular weight of 400-4000) with a sulfonic acid group, a sulfonyl group or a carboxylic acid group is added into the conductive layer, and the bonding aid enhances the covalent connection between the conductive layer and the electroplated metal during electroplating treatment, and simultaneously generates an interaction hydrogen bond with the surface of the insulating substrate so as to enhance the interface bonding strength between the insulating substrate and the metal layer. However, due to the limited covalent connection between the conductive layer and the metal layer and the limited hydrogen bonding effect generated by the groups on the surface of the insulating substrate, the interface bonding strength between the insulating substrate and the metal layer is limited, which still makes it difficult to meet the practical use requirements.
Disclosure of Invention
The invention aims to provide a method for enhancing the interface bonding strength of an insulating substrate and a metal layer, which is characterized in that a modified silane coupling agent-graphene composite liquid is coated on the surface of the insulating substrate, and the interface bonding strength between a conductive layer and the metal layer and between the conductive layer and the insulating substrate is enhanced by utilizing the modified silane coupling agent and hydrolysis products thereof in the modified silane coupling agent-graphene composite liquid, so that the interface bonding strength between the insulating substrate and the metal layer is greatly improved, and the defects in the prior art are overcome.
To achieve the purpose, the invention adopts the following technical scheme:
a method for enhancing the interfacial bond strength of an insulating substrate and a metal layer, comprising the steps of:
A. grafting a modifier to a silane coupling agent to obtain a modified silane coupling agent, and carrying out hydrolysis treatment on the modified silane coupling agent to obtain a modified silane coupling agent hydrolysate, wherein the modifier contains unsaturated nitrogen or sulfur functional groups;
B. mixing the modified silane coupling agent hydrolysate with a graphene solution to obtain a modified silane coupling agent-graphene composite solution, wherein the content of graphene in the modified silane coupling agent-graphene composite solution is 0.01-10% by mass percent;
C. Coating the modified silane coupling agent-graphene composite liquid on the surface of an insulating substrate to obtain a silane coupling agent-graphene composite coating, and drying to form the insulating substrate with a conductive layer, wherein the insulating substrate contains functional groups capable of reacting with hydroxyl groups;
D. electroplating the insulating substrate with the conductive layer to obtain the insulating substrate with the metal layer.
Further, in the step A, the modifier comprises any one of imidazole, 2-methylimidazole, 2-phenylimidazole, benzimidazole, benzotriazole, lysine and thiourea.
Further, in the step A, the silane coupling agent comprises any one of vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri (beta-methoxyethoxy) silane, gamma-aminopropyl triethoxysilane, 3-isocyanatopropyl triethoxysilane and phenylmethyltrimethylsilane.
Further, in the step A, the specific method of the hydrolysis treatment is as follows:
Uniformly mixing a first solvent with water to obtain a first mixed solution;
Stirring the first mixed solution, and dropwise adding a modified silane coupling agent in the stirring process to obtain a second mixed solution;
adjusting the pH value of the second mixed solution to 1.5-6, and stirring the second mixed solution with the adjusted pH value until the second mixed solution is completely transparent to obtain a modified silane coupling agent hydrolysate;
the first solvent includes any one of isopropyl alcohol and ethanol.
Further, in the hydrolysis treatment, the mixing ratio of the first solvent to water is (5-10): 1, calculated according to the mass ratio.
Further, in the step B, the preparation method of the graphene solution includes:
uniformly mixing graphite powder, a surfactant and water, and performing ball milling, ultrasonic treatment, filtration, cleaning and drying to obtain graphene;
and uniformly mixing the graphene with a second solvent to obtain a graphene solution.
In the step B, the mixing ratio of the modified silane coupling agent hydrolysate to the graphene solution is 1 (1-100) according to the mass ratio.
Further, the step C specifically includes:
C1. coating the modified silane coupling agent-graphene composite liquid on the surface of an insulating substrate to obtain a silane coupling agent-graphene composite base layer;
C2. And C1-20 times of repeating the step C4 to obtain the silane coupling agent-graphene composite coating, and drying to form the insulating substrate with the conductive layer.
Further, in the step C2, the drying treatment is specifically performed by drying the upper surface of the silane coupling agent-graphene composite coating;
The drying includes any one of high-energy laser scanning and high-temperature air stream baking.
In the step C, the insulating substrate is a glass substrate, and the step C is specifically that a modified silane coupling agent-graphene composite liquid is coated on the surface of the glass substrate subjected to surface activation treatment to obtain a silane coupling agent-graphene composite coating, and the glass substrate with a conductive layer is formed after drying treatment.
The technical scheme provided by the invention can comprise the following beneficial effects:
1. the modified silane coupling agent in the modified silane coupling agent-graphene composite liquid can form silanol (Si-OH) after being hydrolyzed, and the silanol can react firmly with amino groups, carboxyl groups, hydroxyl groups and other groups on the surface of the insulating substrate to form covalent bonds, so that the interface bonding strength of the modified silane coupling agent in the conductive layer and the insulating substrate is improved. In addition, the covalent bond can also play a role of a bridge, and promote connection between the graphene in the conductive layer and the insulating substrate, so that the interface bonding strength of the graphene in the conductive layer and the insulating substrate is increased. That is, the condensation reaction of the hydrolysis product of the modified silane coupling agent in the conductive layer with the group on the surface of the insulating substrate can improve the interface bonding strength between the conductive layer and the insulating substrate.
2. Because the modifier contains unsaturated nitrogen or sulfur functional groups, the modified silane coupling agent also contains unsaturated nitrogen or sulfur functional groups, and lone pair electrons in the unsaturated nitrogen or sulfur functional groups can form stable coordination bonds (-N-Me bonds or-S-Me bonds, me represents metal atoms) with empty orbitals of metal atoms in the metal layer, so that the interface bonding strength of the modified silane coupling agent in the conductive layer and the metal layer is increased. In addition, the coordination bond also plays a role of a bridge, and promotes the connection between the graphene in the conductive layer and the metal layer, so that the interface bonding strength between the graphene in the conductive layer and the metal layer is increased. That is, the coordination of the unsaturated nitrogen or sulfur functional group of the modified silane coupling agent in the conductive layer and the metal atom in the metal layer can improve the interface bonding strength between the conductive layer and the metal layer.
Detailed Description
The technical scheme provides a method for enhancing the interface bonding strength of an insulating substrate and a metal layer, which comprises the following steps:
A. grafting a modifier to a silane coupling agent to obtain a modified silane coupling agent, and carrying out hydrolysis treatment on the modified silane coupling agent to obtain a modified silane coupling agent hydrolysate, wherein the modifier contains unsaturated nitrogen or sulfur functional groups;
B. mixing the modified silane coupling agent hydrolysate with a graphene solution to obtain a modified silane coupling agent-graphene composite solution, wherein the content of graphene in the modified silane coupling agent-graphene composite solution is 0.01-10% by mass percent;
C. Coating the modified silane coupling agent-graphene composite liquid on the surface of an insulating substrate to obtain a silane coupling agent-graphene composite coating, and drying to form the insulating substrate with a conductive layer, wherein the insulating substrate contains functional groups capable of reacting with hydroxyl groups;
D. electroplating the insulating substrate with the conductive layer to obtain the insulating substrate with the metal layer.
In order to solve the technical problem that the interface bonding strength of an insulating substrate and a metal layer is insufficient in the prior art, the technical scheme provides a method for enhancing the interface bonding strength of the insulating substrate and the metal layer, and the interface bonding strength of the insulating substrate and the metal layer is greatly enhanced by coating a modified silane coupling agent-graphene composite liquid on the surface of the insulating substrate and utilizing the modified silane coupling agent and hydrolysis products thereof in the modified silane coupling agent-graphene composite liquid, so that the practical requirements are met.
Specifically, in the prior art, in order to improve the interface bonding strength between the insulating substrate and the metal layer, a bonding aid of an oligomer (with a molecular weight of 400-4000) with a sulfonic acid group, a sulfonyl group or a carboxyl group is generally added into the conductive layer to enhance the interface bonding strength between the insulating substrate and the metal layer. However, the degree of improving the interface bonding strength between the insulating substrate and the metal layer by adopting the method is limited, and the practical use requirement is difficult to meet. Therefore, the interface bonding strength cannot be improved based on the principle in the technical scheme.
In order to improve the interface bonding strength of the insulating substrate and the metal layer, in the technical scheme, a modified silane coupling agent-graphene composite liquid is obtained by mixing a modified silane coupling agent hydrolysis liquid and a graphene solution, and the modified silane coupling agent-graphene composite liquid is coated on the surface of the insulating substrate to obtain a silane coupling agent-graphene composite coating, and the insulating substrate with a conductive layer is formed after drying treatment. The modified silane coupling agent in the modified silane coupling agent-graphene composite liquid can form silanol (Si-OH) after being hydrolyzed, and the silanol can react firmly with groups such as amino, carboxyl and hydroxyl on the surface of the insulating substrate to form a covalent bond, so that the interface bonding strength of the modified silane coupling agent in the conductive layer and the insulating substrate is improved. In addition, the covalent bond can also play a role of a bridge, and promote connection between the graphene in the conductive layer and the insulating substrate, so that the interface bonding strength of the graphene in the conductive layer and the insulating substrate is increased. That is, the condensation reaction of the hydrolysis product of the modified silane coupling agent in the conductive layer with the group on the surface of the insulating substrate can improve the interface bonding strength between the conductive layer and the insulating substrate.
In addition, since the modifying agent contains an unsaturated nitrogen or sulfur functional group, the modified silane coupling agent also contains an unsaturated nitrogen or sulfur functional group, and a lone pair electron in the unsaturated nitrogen or sulfur functional group can form a stable coordination bond (-N-Me bond or-S-Me bond, me represents a metal atom) with an empty orbit of the metal atom in the metal layer, so that the interface bonding strength of the modified silane coupling agent in the conductive layer and the metal layer is increased. In addition, the coordination bond also plays a role of a bridge, and promotes the connection between the graphene in the conductive layer and the metal layer, so that the interface bonding strength between the graphene in the conductive layer and the metal layer is increased. That is, the coordination of the unsaturated nitrogen or sulfur functional group of the modified silane coupling agent in the conductive layer and the metal atom in the metal layer can improve the interface bonding strength between the conductive layer and the metal layer.
Further, unsaturated nitrogen or sulfur functional groups in the modified silane coupling agent can further stabilize the interface between the conductive layer and the insulating substrate through physical adsorption, so that the connection between graphene in the conductive layer and the insulating substrate is promoted, and the interface bonding strength of the conductive layer and the insulating substrate is improved.
Therefore, in the technical scheme, the interface bonding strength between the conductive layer and the insulating substrate is enhanced by utilizing the modified silane coupling agent and the hydrolysate thereof, and the interface bonding strength between the conductive layer and the metal layer is enhanced by utilizing the modified silane coupling agent, so that the interface bonding strength between the insulating substrate and the metal layer can be greatly improved. In addition, compared with the method for improving the interface bonding strength by using the bonding aid, the method has the advantages that the strength of covalent bonds formed by the reaction of silanol, which is a hydrolysis product of the modified silane coupling agent, with amino, carboxyl, hydroxyl and other groups on the surface of the insulating substrate is higher, and the strength of coordination bonds formed by lone pair electrons in the modified silane coupling agent and metal atoms in the metal layer is higher, so that the interface bonding strength of the insulating substrate and the metal layer is better improved.
Furthermore, as the interface bonding strength of the insulating substrate and the metal layer is improved, the design thickness of the metal layer is improved, and the improvement of the thickness of the metal layer is beneficial to reducing the resistance, so that the metal circuit etched and formed by the metal layer has higher conductivity in the subsequent use process. In addition, due to the improvement of the interface bonding strength between the conductive layer and the insulating substrate and the improvement of the interface bonding strength between the conductive layer and the insulating substrate, the graphene in the conductive layer can fully exert excellent conductivity and mechanical strength, so that the conductive performance and mechanical performance of the whole structure are improved.
Second, the prior art generally uses a dipping method to achieve adhesion of the conductive layer on the insulating substrate, but this method is long in time and difficult to obtain a dense conductive layer.
According to the technical scheme, the coating method is used for replacing the soaking method, the modified silane coupling agent-graphene composite liquid is coated on the surface of the insulating substrate, so that the preparation time of the conductive layer can be shortened, and the content of graphene in the modified silane coupling agent-graphene composite liquid adopted by the coating method is higher (the thickness of the obtained silane coupling agent-graphene composite coating on the surface of the insulating substrate is nano, and the requirement can be met only by a very small amount of graphene, so that even if the content of graphene in the modified silane coupling agent-graphene composite liquid is 0.01%, the content of graphene is relatively higher), the graphene in the modified silane coupling agent-graphene composite liquid can remain on the surface of the insulating substrate after the drying treatment, and in addition, the interface bonding strength of the graphene and the insulating substrate is higher, so that the effects of the two aspects are beneficial to obtaining a denser and thicker conductive layer. Further, due to the fact that the concentration of graphene in the modified silane coupling agent-graphene composite liquid is high (namely the solid content of the modified silane coupling agent-graphene composite liquid is high), even if holes exist on the surface of the insulating substrate, the modified silane coupling agent-graphene composite liquid can penetrate, and the completion degree of electroplating metal on the surface of the substrate and the conductivity and mechanical performance of the whole structure are improved.
It should be noted that, the electroplating method in the present technical solution is a conventional method in the prior art, and will not be described herein. In addition, the emphasis of the present technical solution is that the interface between the reinforced insulating substrate and the metal layer is strongly bonded, so the present technical solution does not describe the process of obtaining patterning before step D or after step D using the etching technique conventional in the art.
Preferably, the insulating substrate includes any one of a glass substrate, a polyamide substrate, and a glass fiber epoxy resin substrate.
Preferably, in the step C, the thickness of the conductive layer is 10-50 nm.
The graphene has excellent conductivity, so that the thickness of the conductive layer is 10-50 nm, high-efficiency electron transmission can be provided, good conductive effect of the conductive layer in electronic equipment or circuits is ensured, the conductive layer has high mechanical strength due to high mechanical strength of the graphene, the conductive layer which is too thin is likely to be damaged easily to influence stability and reliability of the conductive layer in long-term use, the conductive layer can have conductivity and mechanical strength when the thickness of the conductive layer is 10-50 nm, durability of the conductive layer in various application scenes is ensured, the conductive layer and the insulating substrate are combined more tightly when the thickness of the conductive layer is 10-50 nm, and the material cost and production time are increased due to the excessively thick conductive layer. For the reasons mentioned above, therefore, the present solution limits the thickness of the conductive layer so that a cost-effective maximization is achieved while ensuring performance.
Further illustratively, in step A, the modifying agent includes any one of imidazole, 2-methylimidazole, 2-phenylimidazole, benzimidazole, benzotriazole, lysine, and thiourea.
According to the technical scheme, the types of the modifier are optimized, so that the performance of the modified silane coupling agent is guaranteed, the raw materials can be selected according to actual requirements, and the flexibility of the method is improved.
Further illustratively, in step A, the silane coupling agent includes any one of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β -methoxyethoxy) silane, γ -aminopropyl triethoxysilane, 3-isocyanatopropyl triethoxysilane, and phenylmethyltrimethylsilane.
Vinyl triethoxysilane, vinyl trimethoxy silane, vinyl tri (beta-methoxyethoxy) silane, gamma-aminopropyl triethoxysilane, 3-isocyanic acid propyl triethoxysilane and aniline methyl trimethylsilane can be hydrolyzed to generate silanol, so that the performance of the modified silane coupling agent is ensured, the raw materials can be selected according to actual requirements, and the flexibility of the method is improved.
Preferably, the silane coupling agent includes any one of vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris (β -methoxyethoxy) silane.
The carbon chains of the vinyl triethoxysilane, the vinyl trimethoxysilane and the vinyl tri (beta-methoxyethoxy) silane are short, the steric hindrance is small, the hydrophilicity is relatively good, and the hydrolysis reaction rate of the modified silane coupling agent is improved, so that the interface bonding strength of the insulating substrate and the metal layer is improved. In addition, the silane coupling agent has the advantages of good stability, simple preparation method, easy raw material acquisition and low production cost, and is beneficial to reducing the production cost.
Further described, in the step a, the specific method of the hydrolysis treatment is as follows:
Uniformly mixing a first solvent with water to obtain a first mixed solution;
Stirring the first mixed solution, and dropwise adding a modified silane coupling agent in the stirring process to obtain a second mixed solution;
adjusting the pH value of the second mixed solution to 1.5-6, and stirring the second mixed solution with the adjusted pH value until the second mixed solution is completely transparent to obtain a modified silane coupling agent hydrolysate;
the first solvent includes any one of isopropyl alcohol and ethanol.
The silanol produced by hydrolysis of the modified silane coupling agent also undergoes a condensation reaction. That is, the hydrolysis process of the modified silane coupling agent has two reactions of hydrolysis and condensation at the same time, the two reactions are in a competitive state, and the condensation reaction should be controlled to occur in order to ensure that the silanol content in the system is as large as possible. Since water can promote the hydrolysis reaction of the modified silane coupling agent, while isopropanol and ethanol can reduce the condensation reaction of silanol. Therefore, according to the technical scheme, any one of isopropanol and ethanol is uniformly mixed with water to obtain the first mixed solution, so that silanol is generated to the greatest extent.
In addition, when the pH value of the second mixed solution is adjusted to 1.5-6, the difference between the hydrolysis reaction rate and the condensation reaction rate is larger, and the amount of silanol in the system is further increased, so that the interface bonding strength between the conductive layer and the insulating substrate is improved.
When the modified silane coupling agent is not completely hydrolyzed, the second mixed solution with the pH value adjusted is turbid, and when the modified silane coupling agent is completely hydrolyzed, the second mixed solution with the pH value adjusted is completely transparent. Therefore, in order to ensure complete hydrolysis of the modified silane coupling agent, the second mixed solution after the pH adjustment is stirred to be completely transparent in the technical scheme.
Further, in the hydrolysis treatment, the mixing ratio of the first solvent to water is (5-10): 1, calculated according to the mass ratio.
In the technical scheme, the mixing proportion of the first solvent and water is limited, so that the hydrolysis rate of the modified silane coupling agent in the hydrolysis process is maximized, the condensation reaction rate is minimized, the difference between the hydrolysis reaction rate and the condensation reaction rate is maximized, the silanol content of the hydrolysis solution of the modified silane coupling agent is further improved, and the interface bonding strength of the insulating substrate and the metal layer is enhanced.
Further described, in the step B, the preparation method of the graphene solution includes:
uniformly mixing graphite powder, a surfactant and water, and performing ball milling, ultrasonic treatment, filtration, cleaning and drying to obtain graphene;
and uniformly mixing the graphene with a second solvent to obtain a graphene solution.
The principle of the graphene obtained in the step B is that graphite powder, a surfactant and water are mixed, the surfactant is favorable for better dispersing the graphite powder in the water and preventing the graphite powder particles from agglomerating, ball milling is utilized to further refine the graphite powder particles and increase the contact area between the graphite powder particles, the surfactant and the water, subsequent dispersion and stripping are favorable, and the ball milling mixture is subjected to ultrasonic treatment to further strip the graphite powder particles into thinner graphene. The ultrasonic treatment can promote the adsorption of the surfactant on the surfaces of the graphite powder particles and enhance the dispersibility of the graphene, the graphene is separated from the mixture through the filtering operation after the ultrasonic treatment, and the graphene obtained through the filtering is cleaned and dried to remove the surfactant, the moisture and other impurities remained on the surfaces of the graphene so as to improve the purity of the graphene.
In addition, the surfactant is beneficial to the dispersion of the graphite powder and the dispersion of the graphene, long-chain alkyl groups in the molecular structure of the surfactant can be inserted into the interlayer of graphite in the graphite powder, so that interlayer interaction force is weakened, and the graphite powder is promoted to be peeled into the graphene.
Preferably, the second solvent includes any one of ethanol, ethylene glycol, isopropanol, N-methylpyrrolidone, and methylene chloride.
The surfactant comprises any one of sodium dodecyl sulfonate, sodium tetrapropylanilide sulfonate, sodium diisooctyl succinate, sodium dibutyl naphthalene sulfonate, sodium dodecyl sulfate and polyethylene glycol octyl phenyl ether.
Further, in the step B, the mixing ratio of the modified silane coupling agent hydrolysate to the graphene solution is 1 (1-100) according to the mass ratio.
According to the technical scheme, the mixing proportion of the hydrolysis solution of the modified silane coupling agent and the graphene solution is limited, and the content of the modified silane coupling agent and the hydrolysis product thereof is enough, so that the interface bonding strength between the conductive layer and the metal layer and between the conductive layer and the insulating substrate is enhanced and improved, and further the interface bonding strength between the insulating substrate and the metal layer is ensured.
Further described, step C specifically includes:
C1. coating the modified silane coupling agent-graphene composite liquid on the surface of an insulating substrate to obtain a silane coupling agent-graphene composite base layer;
C2. And C1-20 times of repeating the step C4 to obtain the silane coupling agent-graphene composite coating, and drying to form the insulating substrate with the conductive layer.
The modified silane coupling agent and its hydrolysis product play a role in enhancing the bonding force between graphene and the insulating substrate, and graphene is used to form the conductive layer due to its excellent conductive properties. Through 4-20 times of coating, graphene is uniformly and low in distribution in the conductive layer, so that a stable conductive layer with good conductive performance is formed on the surface of the insulating substrate.
In the step C2, the drying treatment is specifically performed by drying the upper surface of the silane coupling agent-graphene composite coating;
The drying includes any one of high-energy laser scanning and high-temperature air stream baking.
In the prior art, the mode of drying treatment mainly adopts that an insulating substrate coated with a modified silane coupling agent-graphene composite liquid is placed in a vacuum drying oven for drying, but in the vacuum drying oven, the volatilization speed of a solvent is limited to a certain extent due to the vacuum state, so that the drying rate is relatively low; in addition, the vacuum drying box is mainly used for removing the solvent in the coating so as to dry and solidify the solvent, and after drying, the coating may still have a certain porosity or loose structure to influence the compactness of the coating.
Furthermore, the high-energy laser beam has high drying speed, the accurate control of the laser can ensure that the coating is heated uniformly, the coating damage caused by local overheating is avoided, the drying efficiency of high-temperature air flow baking is high, and the volatilization path of the solvent can be controlled by adjusting the speed and the direction of the air flow, so that the uniform coating can be formed. Therefore, in order to improve the defects, the drying mode is limited to any one of high-energy laser scanning and high-temperature air flow baking, and the drying mode can obviously accelerate the volatilization speed of the solvent, so that the drying efficiency is improved.
In addition, the upper surface of the silane coupling agent-graphene composite coating is dried, so that the solvent gradually escapes from top to bottom. The directional volatilization mode is favorable for forming a more uniform coating structure, reducing the porosity and the loose structure and improving the compactness and the conductivity of the coating. Further, when the solvent escapes from the surface of the coating, the surface tension of the residual liquid acts on the downward acting force of the graphene in the coating, so that the graphene is more closely attached to the surface of the insulating substrate, and the effect not only enhances the interface bonding strength between the graphene and the insulating substrate, but also helps to improve the stability and durability of the whole coating.
Preferably, the scanning energy of the high-energy laser scanning is 1-10 Kev, and the scanning speed is 50000-100000 pts/s;
the high-temperature airflow baking temperature is 100-150 ℃, and the airflow speed is 1-1.5 m/s.
Further described, the insulating substrate is a glass substrate, and the step C specifically includes:
And coating the modified silane coupling agent-graphene composite liquid on the surface of the glass substrate subjected to the surface activation treatment to obtain a silane coupling agent-graphene composite coating, and drying to form the glass substrate with the conductive layer.
The activation treatment can introduce more hydroxyl-OH on the surface of the glass substrate, so that the hydroxyl-OH is convenient to be condensed with silanol after the hydrolysis of the silane coupling agent to generate chemical bonds, and meanwhile, the activation treatment on the surface of the glass substrate can also increase the surface roughness of the glass substrate or enable the surface of the glass substrate to form a micro-nano structure, thereby being beneficial to forming more firm mechanical anchoring of the modified silane coupling agent on the surface of the glass substrate and further improving the adhesive force and durability of the glass substrate. Therefore, the technical scheme activates the glass substrate, which is beneficial to improving the performance of the product.
The method of the activation treatment may be, but not limited to, plasma cleaning, catalyst activation, high-temperature activation, and the like in the prior art.
The technical scheme of the invention is further described by the following specific embodiments.
Example 1
A. The preparation method comprises the steps of grafting imidazole to vinyl triethoxysilane to obtain a modified silane coupling agent, uniformly mixing isopropanol and water in a mass ratio of 5:1 to obtain a first mixed solution, stirring the first mixed solution, dropwise adding the modified silane coupling agent in the stirring process to obtain a second mixed solution, adjusting the pH value of the second mixed solution to 4, and stirring the second mixed solution with the pH value adjusted to be completely transparent to obtain a modified silane coupling agent hydrolysate;
B. Uniformly mixing graphite powder, sodium dodecyl sulfate and water, performing ball milling, ultrasonic treatment, filtering, cleaning and drying to obtain graphene, uniformly mixing the graphene and ethanol to obtain a graphene solution, and mixing a modified silane coupling agent hydrolysate with the mass ratio of 1:60 with the graphene solution to obtain a modified silane coupling agent-graphene composite solution with the graphene content of 5%;
C. Coating the modified silane coupling agent-graphene composite liquid on the surface of the activated glass substrate to obtain a silane coupling agent-graphene composite base layer, repeatedly coating the modified silane coupling agent-graphene composite liquid on the surface of the activated glass substrate for 10 times to obtain a silane coupling agent-graphene composite coating, and drying the upper surface of the silane coupling agent-graphene composite coating by utilizing high-energy laser scanning with the scanning energy of 5Kev and the scanning speed of 50000pts/s to form a glass substrate with a conductive layer, wherein the thickness of the conductive layer is 20nm;
D. And carrying out copper electroplating treatment on the insulating substrate with the conductive layer to obtain the glass substrate with the metal layer, wherein the electroplating current density is 3A/dm 2, and the electroplating time is 40min.
Example 2
A. Grafting benzimidazole to gamma-aminopropyl triethoxysilane to obtain a modified silane coupling agent, uniformly mixing ethanol and water in a mass ratio of 8:1 to obtain a first mixed solution, stirring the first mixed solution, dropwise adding the modified silane coupling agent in the stirring process to obtain a second mixed solution, adjusting the pH value of the second mixed solution to 5, and stirring the second mixed solution with the pH value adjusted to be completely transparent to obtain a modified silane coupling agent hydrolysate;
B. Uniformly mixing graphite powder, sodium dodecyl sulfate and water, performing ball milling, ultrasonic treatment, filtering, cleaning and drying to obtain graphene, uniformly mixing the graphene and N-methylpyrrolidone to obtain a graphene solution, and mixing a modified silane coupling agent hydrolysate with the mass ratio of 1:50 with the graphene solution to obtain a modified silane coupling agent-graphene composite solution with the graphene content of 8%;
C. Coating the modified silane coupling agent-graphene composite liquid on the surface of a glass fiber epoxy resin substrate to obtain a silane coupling agent-graphene composite base layer, repeatedly coating the modified silane coupling agent-graphene composite liquid on the surface of the glass fiber epoxy resin substrate for 8 times to obtain a silane coupling agent-graphene composite coating, and drying the upper surface of the silane coupling agent-graphene composite coating by using high-temperature nitrogen gas flow with the temperature of 120 ℃ and the gas flow speed of 1.2m/s to form the glass fiber epoxy resin substrate with a conductive layer, wherein the thickness of the conductive layer is 30nm;
D. And carrying out copper electroplating treatment on the glass fiber epoxy resin substrate with the conductive layer to obtain the glass fiber epoxy resin substrate with the metal layer, wherein the electroplating current density is 2A/dm 2, and the electroplating time is 35min.
Example 3
A. the preparation method comprises the steps of grafting benzotriazole to vinyl tri (beta-methoxyethoxy) silane to obtain a modified silane coupling agent, uniformly mixing isopropanol and water in a mass ratio of 10:1 to obtain a first mixed solution, stirring the first mixed solution, dropwise adding the modified silane coupling agent in the stirring process to obtain a second mixed solution, regulating the pH value of the second mixed solution to 3.5, and stirring the second mixed solution with the pH value regulated to be completely transparent to obtain a modified silane coupling agent hydrolysate;
B. Uniformly mixing graphite powder, sodium dodecyl sulfate and water, performing ball milling, ultrasonic treatment, filtering, cleaning and drying to obtain graphene, uniformly mixing the graphene and N-methylpyrrolidone to obtain a graphene solution, and mixing a modified silane coupling agent hydrolysate with the mass ratio of 1:80 with the graphene solution to obtain a modified silane coupling agent-graphene composite solution with the graphene content of 10%;
C. coating the modified silane coupling agent-graphene composite liquid on the surface of a glass substrate to obtain a silane coupling agent-graphene composite base layer, repeatedly coating the modified silane coupling agent-graphene composite liquid on the surface of the glass substrate for 8 times to obtain a silane coupling agent-graphene composite coating, and drying the upper surface of the silane coupling agent-graphene composite coating by using high-temperature nitrogen gas flow with the temperature of 150 ℃ and the gas flow speed of 1.1m/s to form the glass substrate with a conductive layer, wherein the thickness of the conductive layer is 25nm;
D. and carrying out copper electroplating treatment on the glass substrate with the conductive layer to obtain the glass substrate with the metal layer, wherein the electroplating current density is 2.5A/dm 2, and the electroplating time is 30min.
Comparative example 1
Comparative example 1 was identical to the process and starting materials of example 1, except that there were no steps a and B in comparative example 1.
Comparative example 2
Comparative example 2 the modified silane coupling agent was replaced with poly 2-acrylamido-2-methylpropanesulfonic acid, and the remaining raw materials were the same as in example 1, i.e., comparative example 2 was:
A. Uniformly mixing graphite powder, sodium dodecyl sulfate and water, performing ball milling, ultrasonic treatment, filtering, cleaning and drying to obtain graphene, uniformly mixing the graphene and ethanol to obtain a graphene solution with the graphene content of 2 percent, and mixing poly (2-acrylamide) -2-methylpropanesulfonic acid) (a combination aid) with the graphene solution in a mass ratio of 1:60 to obtain a combination aid-graphene composite solution;
B. The method comprises the steps of coating a bonding aid-graphene composite liquid on the surface of an activated glass substrate to obtain a bonding aid-graphene composite base layer, repeating the steps for 10 times to obtain a bonding aid-graphene composite coating, and drying the bonding aid-graphene composite coating by using high-energy laser with scanning energy of 5Kev and scanning speed of 50000pts/s to form a glass substrate with a conductive layer, wherein the thickness of the conductive layer is 20nm;
C. And carrying out copper electroplating treatment on the insulating substrate with the conductive layer to obtain the glass substrate with the metal layer, wherein the electroplating current density is 3A/dm 2, and the electroplating time is 40min.
The surfaces of the insulating substrates having a metal layer prepared in examples and comparative examples were observed, and peel strength between the insulating substrate and the metal layer was tested using a tensile tester, and the test results are shown in the following table:
| Sample of | Surface condition | Peel strength (N/cm) |
| Example 1 | Leveling and compacting | 308.12 |
| Example 2 | Leveling and compacting | 307.61 |
| Example 3 | Leveling and compacting | 304.25 |
| Comparative example 1 | Roughness of | 213.81 |
| Comparative example 2 | Roughness of | 262.44 |
As can be seen from the performance test results in the table, in the embodiment of the present invention, the peel strength of the insulating substrate and the metal layer is significantly higher than that of the insulating substrate and the metal layer in the comparative example, and the peel strength between the insulating substrate and the metal layer is closely related to the interfacial bonding strength between the insulating substrate and the metal layer. Therefore, the interface bonding strength of the insulating substrate and the metal layer in the technical scheme is higher than that of the prior art that the interface bonding strength of the insulating substrate and the metal layer is improved without using the modified silane coupling agent, and is also higher than that of the technical scheme that the interface bonding strength of the insulating substrate and the metal layer is improved by using the bonding aid, but the effect is poor.
The technical principle of the present invention is described above in connection with the specific embodiments. The description is made for the purpose of illustrating the general principles of the invention and should not be taken in any way as limiting the scope of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of this specification without undue burden.
Claims (10)
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