A Parylene coating containing a complex coupling agent and its preparation method and application

Abstract

The present invention belongs to the technical field of Parylene material coatings, and specifically relates to a Parylene coating containing a complex coupling agent, a preparation method thereof, and an application thereof, including a Parylene layer, a complex coupling agent between the Parylene layer and a substrate to be plated, the complex coupling agent comprising a silane coupling agent and an N-containing coupling agent, the mass ratio of the silane coupling agent to the N-containing coupling agent is 1: (0.2-3), and the complex coupling agent is chemically bonded to the Parylene layer and the substrate to be plated, respectively. The present invention can significantly improve adhesion, and at the same time, only a short process time is required to achieve maximum adhesion, and takes into account good heat resistance, excellent uniformity of all samples in a batch, and excellent stability between multiple batches.

Description

Technical Field

[0001] The invention belongs to the technical field of Parylene material coatings, and in particular relates to a Parylene coating containing a complex cross-linking agent, and a preparation method and application thereof. Background Art

[0002] Parylene layer provides various properties, such as protection, lubrication, barrier, insulation and withstand voltage performance. It is a new type of coating made of special materials. Parylene deposition is a vapor deposition process, and parylene itself has a very strong water vapor barrier efficiency. Since Parylene material (polyparaxylene, also known as paralon) is relatively symmetrical (with weak polarity), the bonding force generated during the transformation from gas to solid is like liquid wax turning into solid wax. It can have a little bonding force, but the bonding strength is difficult to be used for industrialization.

[0003] In the prior art, one way to interact with the substrate end is that when the surface roughness of the substrate end material is large, the coupling agent with a smaller molecular weight can penetrate into the pores of the substrate, thereby forming a riveted structure (this bonding method can be understood as a physical mode in more senses). The potential condition of this bonding method is that the molecular weight must match the pores, so in the system, any substance that can control the molecular weight can change the quality of the bonding (it may develop in a good direction or in a bad direction). Therefore, generally speaking, either use coupling agents of different molecular weights to adapt to the substrate. Or use sandblasting or chemical etching processes to make the substrate suitable for the coupling agent.

[0004] However, the coupling agent used in the prior art is a silane coupling agent, which makes the bonding force between the Parylene layer and the substrate to be plated weak, and is easy to fall off, affecting the performance of the Parylene performance of the substrate to be plated.

[0005] Moreover, the conventional silane coupling agent used in this industry is mainly soaking and evaporation. After soaking and evaporation, the silane coupling agent is taken out of the oven. Generally, its adhesion after taking out of the oven cannot be improved immediately. It needs to go through a maturation process, that is, let the silane coupling agent react with water vapor for 3-4 days to ensure that the bonding strength meets industrial requirements. The hundred-grid method is usually used to determine the strength of the bonding strength. Generally, the bonding strength just out of the oven is at the 2-3B level. After 3-4 days of placement, the bonding strength can rise to the 4-5B level. In other words, the process time for improving the adhesion of the existing silane coupling agent is long. Moreover, in the entire cavity, the uniformity of the adhesion of all samples, as well as the stability between batches, are poor.

[0006] It should be noted that this part of the present invention only provides background technology related to the present invention and does not necessarily constitute prior art or known technology. Summary of the invention

[0007] The purpose of the present invention is to overcome the defects of the prior art in that the bonding force between the Parylene layer and the substrate to be plated is weak and the process time for improving the adhesion is long, and to provide a Parylene coating containing a complex coupling agent and a preparation method and application thereof. The Parylene coating containing the complex coupling agent can significantly improve the adhesion, and only requires a short process time to achieve the maximum adhesion, while taking into account good heat resistance, excellent uniformity of all samples in a batch, and excellent stability between multiple batches.

[0008] In order to achieve the above-mentioned object, in a first aspect, the present invention provides a Parylene coating containing a complex coupling agent, comprising a Parylene layer, wherein a complex coupling agent exists between the Parylene layer and a substrate to be plated, the complex coupling agent comprises a silane coupling agent and a N-containing coupling agent, the mass ratio of the silane coupling agent to the N-containing coupling agent is 1:(0.2-3), and the complex coupling agent is chemically bonded to the Parylene layer and the substrate to be plated respectively;

[0009] The silane coupling agent is selected from γ-aminopropyltriethoxysilane, ethyl silicate and

[0010] (abbreviated as A274), (abbreviated as A174), (abbreviated as A151), , , , , , or its corresponding hydrolysis-condensation product.

[0011] The N-containing coupling agent has the following general formula: A-(M)pB, p=0 or 1; the mass content of N in the N-containing coupling agent is 1.5%-20%, preferably 3%-20%.

[0012] Among them, A contains , , , , , , , , , One of the following; wherein the wavy line represents the connection bond with M;

[0013] B contains , , , , , , thiourea group, R1 is selected from H or an alkyl group having 1 to 9 carbon atoms, and R2 is selected from H or an alkyl group having 1 to 9 carbon atoms; wherein the wavy line represents the bond to M;

[0014] M includes 、-CO-、 , , One of the

[0015] Among them, n1 is 1-12; n2 is 1-6, n3 is 1-6; a is 1-6, b is 0-3, c is 0-3, and d is 0-8.

[0016] In some preferred embodiments of the present invention, the N-containing coupling agent is at least one of N-methyl-3-aminopropyltrimethoxysilane, N,N-diethylaminoethyl acrylate, di, N,N'-diethylacrylamide, N-methylallylamine, allyl urea, methacryloyl hydrazide, 4-acryloylmorpholine, diallylamine, triallylamine, allylthiourea, N,N-dimethylallylamine, 4-penten-1-amine, and 2-aminoethyl methacrylate.

[0017] In some preferred embodiments of the present invention, the N-containing coupling agent is at least one of methacryloyl hydrazide, diallylamine, triallylamine, N,N-dimethylallylamine, 4-penten-1-amine, and 2-aminoethyl methacrylate.

[0018] In some preferred embodiments of the present invention, the composite cross-linking agent accounts for 0.5%-32% of the mass of the Parylene layer.

[0019] In a second aspect, the present invention provides a method for preparing a Parylene coating containing a complex coupling agent, which is used to prepare the Parylene coating containing a complex coupling agent described in the first aspect. The method for preparing the Parylene coating containing a complex coupling agent comprises:

[0020] Dissolving the N-containing coupling agent and the silane coupling agent in an alcohol solvent or water and mixing them, or hydrolyzing and condensing the N-containing coupling agent, the silane coupling agent and water to obtain a solution containing a complex coupling agent;

[0021] Then, the substrate to be plated is immersed in a solution containing a complex cross-linking agent for 10-120 minutes, and then dried; and then the Parylene layer is deposited.

[0022] In some preferred embodiments of the present invention, the hydrolysis condensation conditions include: the hydrolysis condensation temperature is room temperature to 60°C, the mass amount of water is 0.1-20wt% of the total amount of N coupling agent and silane coupling agent, and the hydrolysis condensation time is 0.5-24h.

[0023] In some preferred embodiments of the second aspect of the present invention, the mass concentration of the complex coupling agent in the solution containing the complex coupling agent is 0.5wt%-9wt%, preferably 1wt%-5wt%.

[0024] In some preferred embodiments of the second aspect of the present invention, the drying conditions include: a drying temperature of 40-100° C. and a drying time of 1-3 h.

[0025] In a third aspect, the present invention provides a method for preparing a Parylene coating containing a complex coupling agent, which is used to prepare the Parylene coating containing a complex coupling agent described in the first aspect, and the method for preparing the Parylene coating containing a complex coupling agent comprises:

[0026] Dissolving the N-containing coupling agent and the silane coupling agent in an alcohol solvent or water and mixing them, or hydrolyzing and condensing the N-containing coupling agent, the silane coupling agent and water to obtain a solution containing a complex coupling agent;

[0027] Then, under a vacuum environment, the complex coupling agent in the solution containing the complex coupling agent is controlled to volatilize, so that the volatilized complex coupling agent reacts on the surface of the substrate to be plated; then, a Parylene layer is deposited, so that the volatilized complex coupling agent and parylene react on the surface of the substrate to be plated.

[0028] In a fourth aspect, the present invention provides a method for preparing a Parylene coating containing a complex coupling agent, which is used to prepare the Parylene coating containing a complex coupling agent described in the first aspect, and the method for preparing the Parylene coating containing a complex coupling agent comprises:

[0029] Dissolving the N-containing coupling agent and the silane coupling agent in an alcohol solvent or water and mixing them, or hydrolyzing and condensing the N-containing coupling agent, the silane coupling agent and water to obtain a solution containing a complex coupling agent;

[0030] A solution containing a complex coupling agent is placed in an atomizing chamber, and the complex coupling agent is volatilized in a vacuum heating environment, so that the volatilized complex coupling agent reacts on the surface of the substrate to be plated; then a Parylene layer is deposited, so that the complex coupling agent and parylene react on the surface of the substrate to be plated.

[0031] In some preferred embodiments of the fourth aspect of the present invention, the vacuum heating conditions include: a vacuum degree of 50-300 mTorr and a temperature of 40-250°C.

[0032] In a fifth aspect, the present invention provides the use of the Parylene coating containing a complex cross-linking agent described in the first aspect in protecting the surface of a substrate to be plated.

[0033] More preferably, the substrate to be plated is any one of metal, ceramic and glass.

[0034] Beneficial effects:

[0035] It has been found through research that although N-containing coupling agents can improve the adhesion of substrates to be plated (such as metal substrates and ceramic substrates) and Parylene, the reactivity of N-containing coupling agents of different structures is different, especially the reactivity of the N-containing terminal group B. The reactivity can be understood from two dimensions. The first dimension is the ability to catalyze reactions, such as chain transfer reactions, Michael additions, and the ability to catalyze the hydrolysis of siloxanes, etc.; the second dimension is its corrosion ability. Generally speaking, the stronger the nucleophilicity, the stronger the corrosion ability, and the corresponding bonding force (or adhesion) is also stronger. However, some N-containing terminal group B structures are not suitable, the reactivity will be poor, the adhesion cannot be effectively improved, and the heat resistance is poor. Based on this, the present invention is proposed after further research.

[0036] The present invention adopts the above technical scheme, and aims at a N-containing coupling agent with a specific structure having suitable molecular weight, volatility, reactivity and temperature resistance, and can form a complex coupling agent with a specific composition with a specific silane coupling agent to play a synergistic role. On the one hand, the end group B of the N-containing coupling agent has a coordination ability and can form a coordination with the substrate to be plated. The end group A of the N-containing coupling agent contains a carbon-carbon double bond or the end group A does not have a carbon-carbon double bond. The N-containing coupling agent and the silane coupling agent with a double bond react in situ to generate a new coupling agent, and the new coupling agent has a double bond at one end and the ability to connect to the substrate end at the other end. The silane hydrolysis reaction in situ generates a new coupling agent, for example:

[0037] The double bond can react with Parylene by free radicals, and its own molecular weight is suitable, and its penetration performance is strong. It can penetrate into the pores of the substrate. The stronger the riveting ability after the reaction, the stronger the riveting ability can be, thereby forming chemical bonding coupling with the substrate to be plated and Parylene respectively, thereby improving the adhesion. On the other hand, while the N-containing coupling agent forms a coupling itself, it can use the coordination ability and catalytic ability of N in the specific end group B to catalyze the hydrolysis reaction of alkoxysilane in the silane coupling agent, promote the increase of the adhesion structure between the silane coupling agent and the substrate to be plated, thereby accelerating the generation of adhesion, and the N-containing coupling agent with a specific structure has a suitable penetration ability, and can react after complete penetration to form a stable riveting effect, which is beneficial to batch stability and uniformity, thereby achieving an excellent effect of doubling the adhesion. At the same time, only a short process time is required to achieve the maximum adhesion, and the heat resistance is excellent, and it takes into account good heat resistance, excellent uniformity of all samples in a batch, and excellent stability between multiple batches. Among them, the N-containing coupling agent selects a suitable reactive N-containing functional group as B, and cooperates with a silane coupling agent with a suitable structure to balance the penetration rate and reaction rate, which is conducive to synergistically improving the adhesion, especially on surfaces with low roughness, that is, surfaces with smaller or fewer pores. Under the same conditions, if the B group is not suitable, resulting in a reaction rate greater than the penetration rate, then the adhesion will be very poor.

[0038] For example, if a single silane coupling agent such as A174 is used on a surface of a substrate to be plated with high roughness (such as a metal substrate), its molecular weight is too low. Although it can penetrate into the interior of the substrate to be plated, the rivet formed by it is too small and does not block the pores of the substrate to be plated. Therefore, it is pulled apart at a pull, has poor adhesion, and is easy to fall off; while the N in the N-containing coupling agent can form coordination with the metal, especially Cu or Fe. When the N-containing coupling agent and the silane coupling agent such as A174 are used in combination, the N-containing coupling agent can catalyze the hydrolysis reaction of the alkoxysilane in the silane coupling agent, allowing the silane coupling agent to quickly form a three-dimensional network structure, block the pores of the substrate to be plated, and form a physically large-sized riveted structure. At the same time, the N-containing coupling agent can chemically bond with the substrate to be plated, so that it can work together to achieve better adhesion, so that the maximum adhesion can be achieved with a shorter process time, and good heat resistance, excellent uniformity of all samples in a batch, and excellent stability between multiple batches are taken into account.

[0039] The present invention adopts a silane coupling agent and a N-containing coupling agent in a suitable mass ratio, and cooperates with a specific N-containing coupling agent with a suitable N mass content, which can balance the penetration rate and reaction rate, facilitate the synergistic effect to be maximized, and significantly improve the adhesion. This is because if the mass ratio and / or N mass content is not suitable, such as high penetration rate, low reaction rate, slow onset of mechanical properties, and poor adhesion; such as low penetration rate, fast reaction rate, fast onset of mechanical properties, but low final peel strength, poor adhesion, and poor stability. If the proportion of silane coupling agent is low, the degree of crosslinking is low, and the adhesion is poor; if the proportion of silane coupling agent is high, the post-processing operation is cumbersome. DETAILED DESCRIPTION

[0040] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article. Among them, the terms "optional" and "optional" all mean that they may be included or not included (or may be present or not).

[0041] In a first aspect, the present invention provides a Parylene coating containing a complex coupling agent, comprising a Parylene layer, wherein a complex coupling agent exists between the Parylene layer and a substrate to be plated, the complex coupling agent comprises a silane coupling agent and a N-containing coupling agent, the mass ratio of the silane coupling agent to the N-containing coupling agent is 1:(0.2-3), and the complex coupling agent is chemically bonded to the Parylene layer and the substrate to be plated, respectively.

[0042] The mass ratio of the silane coupling agent to the N-containing coupling agent is 1:(0.2-3), and specifically can be 1:0.2, 1:0.3, 1:0.5, 1:0.8, 1:1, 1.0:1.2, 1:1.5, 1:1.7, 1:2.0, 1:2.3, 1:2.5, 1:2.8, 1:3.0, etc. and the range between any two point values.

[0043] The silane coupling agent is selected from γ-aminopropyltriethoxysilane, ethyl silicate and

[0044] , , , , , , , , or its corresponding hydrolysis-condensation product.

[0045] The N-containing coupling agent has the following general formula: A-(M)pB, p=0 or 1; the mass content of N in the N-containing coupling agent is 1.5%-20%, preferably 3%-20%.

[0046] Among them, A contains , , , , , , , , , One of the following; wherein the wavy line represents the connection bond with M;

[0047] B contains , , , , , , thiourea group, R1 is selected from H or an alkyl group having 1 to 9 carbon atoms, and R2 is selected from H or an alkyl group having 1 to 9 carbon atoms; wherein the wavy line represents the bond to M;

[0048] M includes 、-CO-、 , , One of the

[0049] Among them, n1 is 1-12; n2 is 1-6, n3 is 1-6; a is 1-6, b is 0-3, c is 0-3, and d is 0-8.

[0050] The N-containing coupling agent A-(M)pB of the present invention can be obtained by commercial purchase or by synthesis. The synthesis method can refer to any existing synthesis method corresponding to the target structure. As long as the coupling agent of the target chemical formula is obtained, it can be used in the present invention.

[0051] Exemplarily, the N-containing coupling agent is , can be prepared by the following preparation method:

[0052] In a reaction container, vinyl triethoxysilane, tetraethyl orthosilicate, hexamethyldisiloxane, acetic acid, deionized water and isopropanol are added, and stirred at a certain temperature (such as 20-30°C) to obtain a reaction solution. 3-aminopropyl triethoxysilane is neutralized with acetic acid, and the obtained neutralized solution is added to the above reaction solution and continued to be stirred. After the reaction is completed, the solvent is removed by rotary evaporation, and the hydrolyzate is dissolved in toluene, washed with deionized water, dried, and spin-dried.

[0053] In some preferred embodiments of the present invention, the N-containing coupling agent is at least one of N-methyl-3-aminopropyltrimethoxysilane, N,N-diethylaminoethyl acrylate, di, N,N'-diethylacrylamide, N-methylallylamine, allylurea, methacryloylhydrazide, 4-acryloylmorpholine, diallylamine, triallylamine, allylthiourea, N,N-dimethylallylamine, 4-pentene-1-amine, and 2-aminoethyl methacrylate. The use of this preferred solution in combination with a silane coupling agent is beneficial to making up for the aging resistance to a certain extent, and is more beneficial to improving adhesion, further shortening the process time to achieve maximum adhesion, and further improving the uniformity of all samples in a batch and the stability between batches.

[0054] In some preferred embodiments of the present invention, the N-containing coupling agent is at least one of methacryloyl hydrazide, diallylamine, triallylamine, N,N-dimethylallylamine, 4-pentene-1-amine, and 2-aminoethyl methacrylate. The scheme of introducing the preferred N-containing coupling agent has good catalytic performance, is mainly used to catalyze the hydrolysis and condensation reaction of the silane coupling agent, is more conducive to improving the binding force, and can make the complex coupling agent have a suitable molecular weight, volatility and corrosiveness, is more conducive to improving adhesion, further shortening the process time to achieve maximum adhesion, and further helps to improve the uniformity of all samples in a batch and the stability between batches.

[0055] Preferably, in the present invention, when the silane coupling agent contains oxime and acetyl groups, oxime and acetic acid will be released during the hydrolysis process. These two small molecules will contribute to the corrosion of the substrate and further promote the generation of mechanical strength.

[0056] In some preferred embodiments of the present invention, the compound coupling agent is 0.5%-32% of the mass of the Parylene layer, for example, it can be 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 9.0%, 10.0%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, etc. and the range between any two point values, for example, it can be preferably 0.5%-6.0%. The appropriate ratio of compound coupling agent to Parylene can increase the total content of Parylene in the film layer, while ensuring the strong adhesion of parylene, which is more conducive to the barrier performance of the Parylene coating.

[0057] The coupling agent of the prior art generally cannot improve the adhesion immediately after being attached and taken out of the oven. It needs to go through a maturation process, that is, it needs to react with the coupling agent and water vapor for 3-4 days before the bonding strength can meet industrial requirements (for example, usually, the field uses the hundred-grid method to determine the strength of the bonding strength. For example, when using A174, the bonding strength is 2-3B just out of the oven, and after 3-4 days, the bonding strength can rise to the level of 4-5B).

[0058] By using the specific composite coupling agent of the present invention, it is possible to achieve a state where the adhesion of the composite coupling agent is at the maximum value after it comes out of the oven (for example, the bonding strength can immediately reach 4-5B after it comes out of the oven, and the bonding strength will not increase after being placed for a period of time). This is mainly due to the fact that N in the N-containing coupling agent can undergo Michael addition reaction with double bonds and potential free radical chain transfer reaction, and the N-containing coupling agent can catalyze the hydrolysis reaction of the silane coupling agent. The superposition of multiple possible reactions accelerates the overall reaction rate and shortens the processing time for improving adhesion.

[0059] In a second aspect, the present invention provides a method for preparing a Parylene coating containing a complex coupling agent, which is used to prepare the Parylene coating containing a complex coupling agent described in the first aspect. The method for preparing the Parylene coating containing a complex coupling agent comprises:

[0060] Dissolving the N-containing coupling agent and the silane coupling agent in an alcohol solvent or water and mixing them, or hydrolyzing and condensing the N-containing coupling agent, the silane coupling agent and water to obtain a solution containing a complex coupling agent;

[0061] Then, the substrate to be plated is immersed in a solution containing a complex cross-linking agent for 10-120 minutes, and then dried; and then the Parylene layer is deposited.

[0062] The specific type of the alcohol solvent in the present invention can be any type as long as it can dissolve the N-containing coupling agent and the silane coupling agent, for example, it can be isopropyl alcohol.

[0063] In some preferred embodiments of the present invention, the conditions for the hydrolysis condensation include: the temperature for the hydrolysis condensation is from room temperature to 60°C.

[0064] Further preferably, in the hydrolysis condensation, the mass amount of water is 0.1-20wt% of the total amount of the N-containing coupling agent and the silane coupling agent. The degree of hydrolysis can be regulated by controlling the amount of water in the hydrolysis condensation, for example, partial hydrolysis can be achieved by making the water content less than the molar ratio of the silicon-oxygen-carbon bond.

[0065] More preferably, the hydrolysis condensation time is 0.5-24 h, more preferably 1-24 h, more preferably 1-3.5 h.

[0066] In some preferred embodiments of the second aspect of the present invention, the mass concentration of the complex coupling agent in the solution containing the complex coupling agent is 0.5wt%-9wt%, preferably 1wt%-5wt%.

[0067] In some preferred embodiments of the second aspect of the present invention, the drying conditions include: a drying temperature of 40-100° C. and a drying time of 1-3 h.

[0068] In a third aspect, the present invention provides a method for preparing a Parylene coating containing a complex coupling agent, which is used to prepare the Parylene coating containing a complex coupling agent described in the first aspect, and the method for preparing the Parylene coating containing a complex coupling agent comprises:

[0069] Dissolving the N-containing coupling agent and the silane coupling agent in an alcohol solvent or water and mixing them, or hydrolyzing and condensing the N-containing coupling agent, the silane coupling agent and water to obtain a solution containing a complex coupling agent;

[0070] Then, under a vacuum environment, the complex coupling agent in the solution containing the complex coupling agent is controlled to volatilize, so that the volatilized complex coupling agent reacts on the surface of the substrate to be plated; then, a Parylene layer is deposited, so that the volatilized complex coupling agent and parylene react on the surface of the substrate to be plated.

[0071] In some preferred embodiments of the third aspect of the present invention, the conditions for volatilization of the complex coupling agent include: vacuum degree of 50-300 mTorr, temperature of 40-250° C., and time of 0.5-5 h.

[0072] In a fourth aspect, the present invention provides a method for preparing a Parylene coating containing a complex coupling agent, which is used to prepare the Parylene coating containing a complex coupling agent described in the first aspect, and the method for preparing the Parylene coating containing a complex coupling agent comprises:

[0073] Dissolving the N-containing coupling agent and the silane coupling agent in an alcohol solvent or water and mixing them, or hydrolyzing and condensing the N-containing coupling agent, the silane coupling agent and water to obtain a solution containing a complex coupling agent;

[0074] The solution containing the complex coupling agent is placed in the atomization chamber, and the complex coupling agent is volatilized in a vacuum heating environment, so that the volatilized complex coupling agent reacts on the surface of the substrate to be plated; then the Parylene layer is deposited, so that the complex coupling agent and parylene react on the surface of the substrate to be plated. Among them, the reaction of the volatilized complex coupling agent on the surface of the substrate to be plated has several meanings: first, it may be a coordination reaction with the metal, second, it causes slight corrosion to the metal, and third, small molecules penetrate; then free radical reaction occurs under the action of parylene.

[0075] In the third and fourth aspects of the present invention, the preparation process of the complex coupling agent is the same as that of the second aspect, and will not be repeated here.

[0076] In the third and fourth aspects of the present invention, under vacuum environment, the complex coupling agent volatilizes, and the N-containing coupling agent and the silane coupling agent volatilize simultaneously or the N-containing coupling agent and the silane coupling agent volatilize in steps (for example, the silane coupling agent volatilizes first, and the N-containing coupling agent volatilizes later). It can be heated and / or pressurized by opening and closing two AP devices contained in the vacuum evaporation equipment in coordination with the heating and pressurizing mechanism on the AP device to achieve simultaneous volatilization or step-by-step volatilization; after volatilization, it can stay for a certain time (such as 0.5-3h) and then deposit the Parylene layer, or directly deposit the Parylene layer without staying. Preferably, it is volatilized in steps, that is, first volatilize any one of the N-containing coupling agent and the silane coupling agent, and then volatilize the other; for example, first volatilize the silane coupling agent, and then volatilize the N-containing coupling agent; in this way, it can be ensured that the N-containing coupling agent is a small molecule with better penetration ability. If they evaporate at the same time (such as the complex cross-linking agents formed by hydrolysis and condensation need to evaporate at the same time), then after the molecular weight increases, during the phase change process, there is only electrostatic adsorption but no riveting force, which causes a certain loss in bonding strength and bonding reliability.

[0077] In some preferred embodiments of the fourth aspect of the present invention, the vacuum heating conditions include: vacuum degree of 50-300 mTorr, temperature of 40-250° C., and time of 0.5-5 h.

[0078] The N-containing coupling agent of the present invention has a suitably small molecular weight, is easily vaporized (has a low boiling point), and can balance the reaction activity and penetration ability (it cannot react before penetration, otherwise the bonding will not be strong, and it must wait until the N-containing coupling agent and the silane coupling agent penetrate at the same time to have suitable catalytic activity), thereby significantly improving the adhesion. At the same time, only a short process time is required to achieve the maximum adhesion, and good heat resistance, excellent uniformity of all samples in a batch, and excellent stability between multiple batches are taken into account.

[0079] In the volatilization method or the atomization method, for relatively volatile silane coupling agents such as A174, since one end of A174 is a trimethoxysilane group, the group must react with water vapor to take effect, but the reaction of trimethoxysilane and water is relatively slow, and it usually takes 7 days to achieve complete reaction. Therefore, in the absence of the introduction of N-containing coupling agents, the production efficiency will be greatly reduced; and due to the extremely strong water barrier properties of parylene, the probability of contact between silane and water vapor is also reduced; therefore, in the absence of a catalyst, the slower reaction time and the lower contact possibility with water vapor make A174 extremely difficult to take effect on many substrates to be plated. The present invention adopts N-containing coupling agents and silane coupling agents for appropriate compounding, which can catalyze the reaction of A174, greatly improve production efficiency, significantly improve adhesion, and only need a shorter process time to achieve maximum adhesion, and take into account good heat resistance, excellent uniformity of all samples in a batch, and excellent stability between multiple batches.

[0080] In the preparation methods of the second to fourth aspects of the present invention, the mass ratio of the complex cross-linking agent and the Parylene layer in the obtained Parylene coating can be controlled by controlling the feeding amount of each raw material.

[0081] In the second to fourth aspects of the present invention, the Parylene layer is deposited by CVD using Parylene N, Parylene C, Parylene F or Parylene HT as raw material, and the deposition process can be carried out by referring to the prior art, which is the prior art and will not be described in detail here.

[0082] In a fifth aspect, the present invention provides the use of the Parylene coating containing a complex cross-linking agent described in the first aspect in protecting the surface of a substrate to be plated.

[0083] In some preferred embodiments of the present invention, the substrate to be plated is any one of metal, ceramic, and glass. The metal may be, for example, copper, silver, gold-plated, stainless steel, etc. The ceramic may be, for example, an oxide or a nitride.

[0084] The embodiments of the present invention are described in detail below, which are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention.

[0085] Example 1

[0086] The N-containing coupling agent is N-methyl-3-aminopropyltrimethoxysilane, and the mass content of N in the N-containing coupling agent is 7.24%.

[0087] Silane coupling agent is .

[0088] A Parylene coating containing a complex coupling agent is prepared by the following preparation method:

[0089] Preparation of complex coupling agent: Place N-containing coupling agent and silane coupling agent in isopropanol, add water, stir and mix at room temperature for 2 hours to obtain isopropanol solution containing complex coupling agent. The mass ratio of silane coupling agent to N-containing coupling agent is 3:1, and the mass amount of water is 3.90wt% of the total amount of N-containing coupling agent and silane coupling agent. The mass concentration of complex coupling agent in isopropanol solution containing complex coupling agent is 2.50wt%;

[0090] Then, the substrate to be plated is immersed in an isopropanol solution containing a complex coupling agent for 1 hour, and then dried. The drying conditions include: a drying temperature of 65° C. and a time of 1 hour. Then, a Parylene layer is deposited by CVD using Parylene N as a raw material. The amount of the complex coupling agent is 1.5% of the mass of the Parylene layer.

[0091] Example 2

[0092] The method of Example 1 is referred to, except that the mass ratio of the silane coupling agent to the N-containing coupling agent is 1:1.

[0093] Example 3

[0094] The method of Example 1 was followed, except that the N-containing coupling agent was N,N-diethylaminoethyl acrylate (commercial manufacturer: Sinopharm Chemical Reagent Co., Ltd.) The mass content of N in the N-containing coupling agent was 8.18%.

[0095] Example 4

[0096] The method of Example 1 was followed, except that the N-containing coupling agent was di(3-trimethoxysilylpropyl)amine (commercial manufacturer: Sinopharm Chemical Reagent Co., Ltd.) The mass content of N in the N-containing coupling agent was 4.09%.

[0097] Example 5

[0098] The method of Example 1 was followed, except that the N-containing coupling agent was dimethylaminoethyl acrylate (commercial manufacturer: Sinopharm Chemical Reagent Co., Ltd.), and the mass content of N in the N-containing coupling agent was 9.78%.

[0099] Example 6

[0100] The method of Example 1 is carried out, except that the silane coupling agent is:

[0101] (Commercial manufacturer: Momentive High-Tech Materials Group).

[0102] Example 7

[0103] The method of Example 1 is carried out, except that the silane coupling agent is:

[0104] (Commercial manufacturer: Sinopharm Chemical Reagent Co., Ltd.).

[0105] Example 8

[0106] The method of Example 1 was followed, except that the silane coupling agent was vinyltributylidene oxime silane (commercial manufacturer: Sinopharm Chemical Reagent Co., Ltd.).

[0107] Example 9

[0108] The method of Example 1 was followed, except that the silane coupling agent was tri(isoallyloxy)vinylsilane (commercial manufacturer: Sinopharm Chemical Reagent Co., Ltd.).

[0109] Example 10

[0110] The method of Example 1 is referred to, except that the amount of the compound coupling agent is adjusted to make it 7% of the mass of Parylene.

[0111] Embodiment 11

[0112] The method of Example 1 is referred to, except that after preparing the complex coupling agent, the preparation method of the reaction is different, as follows:

[0113] In a vacuum environment, the vacuum degree is 250mTorr, and the complex coupling agent is naturally volatilized, wherein the silane coupling agent and the N-containing coupling agent are volatilized step by step by opening and closing two AP devices contained in the vacuum evaporation equipment: the silane coupling agent is volatilized first, and then the N-containing coupling agent is volatilized, and the volatilization temperature is room temperature, so that the volatilized complex coupling agent reacts on the surface of the substrate to be plated for 2h; after staying for 2h, a Parylene layer is deposited by CVD (the deposition process is the same as that in Example 1), so that the volatilized complex coupling agent and parylene react on the surface of the substrate to be plated.

[0114] Example 12

[0115] The method of Example 1 is referred to, except that the preparation method is different, as follows:

[0116] The N-containing coupling agent and the silane coupling agent are partially hydrolyzed and condensed by reducing the content of added water (i.e., not completely hydrolyzed, and some alkoxy silicon functional groups are retained) to obtain a complex coupling agent;

[0117] A solution containing a complex coupling agent is placed in an atomizing chamber, and the complex coupling agent is volatilized in a vacuum heating environment with a vacuum degree of 250 mTorr, a temperature of 150° C., and a heating time of 3 hours, so that the complex coupling agent is reacted on the surface of the substrate to be plated; then, a Parylene layer is deposited by CVD (the deposition process is the same as in Example 1), so that the complex coupling agent and parylene react on the surface of the substrate to be plated.

[0118] Example 13

[0119] The method of Example 1 is referred to, except that in the immersion method of Example 1, the key process parameters are adjusted: the hydrolysis time is adjusted from 2 h to 4 h.

[0120] Embodiment 14

[0121] The method of Example 11 is used, except that, the preparation of the complex coupling agent is as follows: the N-containing coupling agent, the silane coupling agent and water are hydrolyzed and condensed at 25° C. (room temperature) for 0.5 h to form a complex coupling agent hydrolysis condensate; wherein, the amount of the N-containing coupling agent and the silane coupling agent is the same as that of Example 1, and the mass amount of water is 10wt% of the total amount of the N-containing coupling agent and the silane coupling agent;

[0122] In the vacuum volatilization step of Example 11, the hydrolysis condensate of the complex coupling agent is volatilized by opening and closing two AP devices contained in the vacuum evaporation equipment and heating and pressurizing to control the volatilization (equivalent to the simultaneous volatilization of the silane coupling agent and the N-containing coupling agent), so that the volatilized complex coupling agent reacts on the surface of the substrate to be plated for 2 hours; after staying for 2 hours, the Parylene layer is deposited by CVD (the deposition process is the same as that of Example 1), so that the volatilized complex coupling agent and parylene react on the surface of the substrate to be plated.

[0123] Embodiment 15

[0124] The method of Example 1 is carried out, except that the N-containing coupling agent is , N content is 1.87%. The N-containing coupling agent is prepared by the following preparation method:

[0125] In a three-necked flask, 43g of vinyl triethoxysilane (Sinopharm Chemical Reagent Co., Ltd.), 47.1g of tetraethyl orthosilicate (Sinopharm Chemical Reagent Co., Ltd.), 110.0g of hexamethyldisiloxane (Sinopharm Chemical Reagent Co., Ltd.), 10g of acetic acid (Sinopharm Chemical Reagent Co., Ltd.), 40g of deionized water and 681g of isopropanol (Sinopharm Chemical Reagent Co., Ltd.) were added, and stirred at 25°C for 1h to obtain a reaction solution. 3-aminopropyl triethoxysilane was neutralized with 14g of acetic acid, and the obtained neutralized solution was added to the above reaction solution and continued to stir for 1h. After the reaction was completed, the solvent was removed by rotary evaporation, and the hydrolyzate was dissolved in toluene, washed with deionized water three times, dried, and spin-dried to obtain a silane coupling agent containing N, vinyl, and silicone as a skeleton.

[0126] Example 16

[0127] The method of Example 1 is carried out, except that the silane coupling agent is (Commercial manufacturer: Sinopharm Chemical Reagent Co., Ltd.).

[0128] Embodiment 17

[0129] The method of Example 1 is carried out, except that the silane coupling agent is (Commercial manufacturer: Sinopharm Chemical Reagent Co., Ltd.).

[0130] Embodiment 18

[0131] The method of Example 1 was followed, except that the N-containing coupling agent was dimethylaminoethyl methacrylate (commercial manufacturer: Sinopharm Chemical Reagent Co., Ltd.), wherein the N content was 8.92%.

[0132] Embodiment 19

[0133] The method of Example 1 is carried out, except that the N-containing coupling agent is (Commercial manufacturer: Sinopharm Chemical Reagent Co., Ltd.), with an N content of 14.4%.

[0134] Embodiment 20

[0135] The method of Example 1 was followed, except that the N-containing coupling agent was 3-aminopropyltrimethoxysilane (commercial manufacturer: Sinopharm Chemical Reagent Co., Ltd.), wherein the N content was 7.81%.

[0136] Embodiment 21

[0137] The method of Example 1 is carried out, except that the N-containing coupling agent is (Commercial manufacturer: Nanjing Yaoshi Technology Co., Ltd.), the N content of which is 24.6%.

[0138] Embodiment 22

[0139] The method of Example 1 is carried out, except that the N-containing coupling agent is (Commercial manufacturer: Sinopharm Chemical Reagent Co., Ltd.), N content is 9.03%.

[0140] Embodiment 23

[0141] The method of Example 1 is carried out, except that the N-containing coupling agent is (Commercial manufacturer: Nanjing Yaoshi Technology Co., Ltd.), N content is 28%.

[0142] Embodiment 24

[0143] The method of Example 1 is carried out, except that the N-containing coupling agent is (Commercial manufacturer: Nanjing Yaoshi Technology Co., Ltd.), N content is 7.41%.

[0144] Comparative Example 1

[0145] The method of Example 1 was followed, except that no N-containing coupling agent was added.

[0146] Comparative Example 2

[0147] The method of Example 1 was followed, except that no silane coupling agent was added.

[0148] Comparative Example 3

[0149] The method of Example 1 was followed, except that the N-containing coupling agent was N-methylpiperidine (commercial manufacturer: Sinopharm Chemical Reagent Co., Ltd.), and the N mass content thereof was 14.12%.

[0150] Comparative Example 4

[0151] The method of Example 1 is referred to, except that the mass ratio of the silane coupling agent to the N-containing coupling agent is 1:7.

[0152] Test Case

[0153] The Parylene coatings obtained in the above embodiments and comparative examples were subjected to various performance tests shown in Table 1, and the results are shown in Table 1, Table 2, and Table 3, respectively. The bonding strength was tested according to the standard ASTM D3359 hundred-grid test method, and the bonding strength grades are shown in Table 1, Table 2, and Table 3. The higher the grade number, the stronger the bonding strength; the hundred-grid test method includes: drawing lines on the coating surface according to the standard, and then adhering with a specific tape to see whether the coating can be removed by the tape to judge the bonding strength of the coating. And because the atmosphere at different heights in the CVD deposition furnace of the Parylene coating may be different, the present invention divides the furnace into 5 different heights in the corresponding CVD deposition process in each example, and places corresponding slides (i.e., glass slides, stainless steel sheets, aluminum sheets, gold-plated sheets, and copper sheets) at different heights for coating to obtain five groups of samples. Five groups of grade data are obtained by testing according to the above standard, and the data with higher grade occurrence frequency is taken as the final data measured; illustratively, if the five groups of grade data of the glass slide are 5B, 5B, 4B, 4B, and 5B, the data with higher occurrence frequency is 5B, which is the final data measured.

[0154] Among them, the storage conditions for 2 hours or 3 days out of the oven are storage at room temperature of 25°C and humidity of 50%. After the target storage time, the bonding strength is tested according to the above standards.

[0155] The bonding strength at 150℃ for 2h refers to the bonding strength measured according to the above standard after being baked for 3 days and aged in a drying oven at 150℃ for 2h.

[0156] Double 85% refers to the bonding strength measured according to the above standard after aging for 120 hours in an environment with a temperature of 85°C and a humidity of 85% for 3 days after being baked.

[0157] Among them, batch stability is characterized by testing the binding force of corresponding slides (i.e. glass slides, stainless steel, aluminum slides, gold-plated slides, copper slides) at the upper outer, upper inner, middle outer, middle inner, lower outer, and lower inner positions of multiple batches of accompanying plating slides in the furnace. The uniformity index within a batch is characterized by testing the binding force of corresponding slides at the upper outer, upper inner, middle outer, middle inner, lower outer, and lower inner positions of the accompanying plating slides in the furnace.

[0158]

[0159]

[0160] Table 3 (NA means the initial test value is 0)

[0161]

[0162] From the above results, it can be seen that, compared with the comparative example, the embodiment scheme of the present invention can significantly improve the adhesion, and at the same time, only a short process time is required to achieve the maximum adhesion, and good heat resistance, excellent uniformity of all samples in a batch, and excellent stability between multiple batches are taken into account. Further, according to Example 1 and Examples 2-24, it can be seen that the preferred specific compounding scheme of the present invention is more conducive to improving adhesion, taking into account good heat resistance, excellent uniformity of all samples in a batch, and excellent stability between multiple batches.

[0163] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A Parylene coating containing a complex coupling agent, comprising a Parylene layer, characterized in that: There is a complex coupling agent between the Parylene layer and the substrate to be plated, the complex coupling agent comprises a silane coupling agent and a N-containing coupling agent, the mass ratio of the silane coupling agent to the N-containing coupling agent is 1:(0.2-3), and the complex coupling agent is chemically bonded to the Parylene layer and the substrate to be plated respectively; The silane coupling agent is selected from γ-aminopropyltriethoxysilane and , , , , , , , , At least one of or its corresponding hydrolysis condensate; The N-containing coupling agent includes the following general formula: A-(M)pB, p=0 or 1; the mass content of N in the N-containing coupling agent is 1.5%-20%; wherein, A includes , , , , , , , , , One of the following; wherein the wavy line represents a connecting bond; B contains , , , , , , thiourea group, R1 is selected from H or an alkyl group having 1 to 9 carbon atoms, and R2 is selected from H or an alkyl group having 1 to 9 carbon atoms; wherein the wavy line represents a connecting bond; M includes 、-CO-、 , , One of the following; Among them, n1 is 1-12; n2 is 1-6, n3 is 1-6; a is 1-6, b is 0-3, c is 0-3, and d is 0-8.

2. The Parylene coating containing a complex coupling agent according to claim 1, characterized in that: The N-containing coupling agent is at least one of N-methyl-3-aminopropyltrimethoxysilane, N,N-diethylaminoethyl acrylate, di(3-trimethoxysilylpropyl)amine, dimethylaminoethyl acrylate, N,N'-dimethylacrylamide, N,N'-diethylacrylamide, N-methylallylamine, allylurea, methacryloylhydrazide, 4-acryloylmorpholine, diallylamine, triallylamine, allylthiourea, N,N-dimethylallylamine, 4-pentene-1-amine, and 2-aminoethyl methacrylate.

3. The Parylene coating containing a complex coupling agent according to claim 2, characterized in that: The N-containing coupling agent is at least one of methacryloyl hydrazide, diallylamine, triallylamine, N,N-dimethylallylamine, 4-penten-1-amine, and 2-aminoethyl methacrylate.

4. The Parylene coating containing a complex coupling agent according to claim 1, characterized in that: The compound coupling agent accounts for 0.5%-32% of the mass of the Parylene layer.

5. Use of the Parylene coating containing a complex cross-linking agent as claimed in any one of claims 1 to 4 in the surface protection of a substrate to be plated, wherein the substrate to be plated is any one of metal, ceramic and glass.

6. A method for preparing a Parylene coating containing a complex coupling agent, characterized in that: It is used to prepare the Parylene coating containing a complex coupling agent as described in any one of claims 1 to 4, and the preparation method of the Parylene coating containing a complex coupling agent comprises: Dissolving the N-containing coupling agent and the silane coupling agent in an alcohol solvent or water and mixing them, or hydrolyzing and condensing the N-containing coupling agent, the silane coupling agent and water to obtain a solution containing a complex coupling agent; Then, the substrate to be plated is immersed in a solution containing a complex cross-linking agent for 10-120 minutes, and then dried; and then the Parylene layer is deposited.

7. The method for preparing a Parylene coating containing a complex coupling agent according to claim 6, characterized in that: The mass concentration of the complex coupling agent in the solution containing the complex coupling agent is 0.5wt%-9wt%; and / or, The conditions for the hydrolysis and condensation include: the hydrolysis and condensation temperature is room temperature to 60°C, the mass amount of water is 0.1-20wt% of the total amount of N coupling agent and silane coupling agent, and the hydrolysis and condensation time is 0.5-24h; the conditions for the drying include: the drying temperature is 40-100°C, and the time is 1-3h.

8. A method for preparing a Parylene coating containing a complex coupling agent, characterized in that: It is used to prepare the Parylene coating containing a complex coupling agent as described in any one of claims 1 to 4, and the preparation method of the Parylene coating containing a complex coupling agent comprises: Dissolving the N-containing coupling agent and the silane coupling agent in an alcohol solvent or water and mixing them, or hydrolyzing and condensing the N-containing coupling agent, the silane coupling agent and water to obtain a solution containing a complex coupling agent; Then, under a vacuum environment, the complex coupling agent in the solution containing the complex coupling agent is controlled to volatilize, so that the volatilized complex coupling agent reacts on the surface of the substrate to be plated; then, a Parylene layer is deposited, so that the volatilized complex coupling agent and parylene react on the surface of the substrate to be plated.

9. A method for preparing a Parylene coating containing a complex coupling agent, characterized in that: It is used to prepare the Parylene coating containing a complex coupling agent as described in any one of claims 1 to 4, and the preparation method of the Parylene coating containing a complex coupling agent comprises: Dissolving the N-containing coupling agent and the silane coupling agent in an alcohol solvent or water and mixing them, or hydrolyzing and condensing the N-containing coupling agent, the silane coupling agent and water to obtain a solution containing a complex coupling agent; A solution containing a complex coupling agent is placed in an atomizing chamber, and the complex coupling agent is volatilized in a vacuum heating environment, so that the volatilized complex coupling agent reacts on the surface of the substrate to be plated; then a Parylene layer is deposited, so that the complex coupling agent and parylene react on the surface of the substrate to be plated.

10. The method for preparing a Parylene coating containing a complex coupling agent according to claim 9, characterized in that: The vacuum heating conditions include: vacuum degree of 50-300 mTorr and temperature of 40-250°C.

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