High-stability metal surface cleaning degumming agent

Abstract

The invention relates to the technical field of metal material chemical cleaning, and discloses a high-stability metal surface cleaning degumming agent, which comprises a high-polarity organic solvent, a perfluoroalkyl siloxane block copolymer, an organic amine auxiliary agent and a polar diluent, the perfluoroalkyl siloxane block copolymer is distributed in the polar diluent to form microemulsion particles with the particle size of 80-150 nm, and an interface barrier layer with the thickness of 5-20 nm is constructed on a gas-liquid interface in a directional arrangement mode. According to the invention, an interface shielding mechanism is utilized to inhibit mass evaporation loss of a high-polarity organic solvent under an operation condition, and environmental moisture permeation is synchronously blocked; and a curing adhesive layer on the metal surface is forcibly replaced through the displacement adsorption effect of the copolymer on a liquid-solid interface, the environmental stability of a degumming system is improved, and long-term stable operation of a cleaning process window is guaranteed.

Description

Technical Field

[0001] This invention belongs to the field of chemical cleaning technology for metal materials, and particularly relates to a highly stable metal surface cleaning and degumming agent. Background Technology

[0002] Currently, removing residual cured adhesives or protective grease from metal surfaces involves chemical cleaning processes. Conventional techniques utilize highly polar organic solvents combined with strong alkalis or surfactants to achieve degumming through dissolution and swelling. In large-scale production lines, degumming tanks are typically at 60°C. Up to 80 The high-temperature open state causes the polar solvent to continuously evaporate and cause a shift in the component ratio. The highly polar system absorbs atmospheric moisture and carbon dioxide, which induces solvent hydrolysis and alkalinity neutralization, shortens the life of the bath, and causes pitting corrosion on the surface of the metal substrate.

[0003] Besides the aforementioned environmental damage, existing degumming solutions have shortcomings in their component logic and stripping control methods. For example, Chinese invention patent CN108677195B discloses a degumming method for adhesive metals, using a dichloromethane, alumina, and sulfuric acid system. It employs strong acid catalysis and solvent dissolution for degumming. This technical approach, based on highly volatile components and strong corrosiveness, is inadequate for applications involving 60... Up to 80 In high-temperature open-air conditions, the violent escape of low-boiling-point components such as dichloromethane causes component drift in the cleaning solution, resulting in a decrease in cleaning efficiency over time. Strong acid environments damage the physicochemical properties of precision metal parts, inducing secondary oxidation or electrochemical pitting. Such technologies remain at the level of homogeneous reaction based on dissolution and diffusion, lacking a self-shielding mechanism at the gas-liquid interface and a liquid-solid interface stripping logic. Colloidal substances quickly become saturated upon entering the bulk phase, limiting the cumulative degumming load of the bath solution and making it difficult to meet the consistent packaging quality requirements of high-reliability electronic devices.

[0004] Therefore, the technical problem to be solved by this invention is how to construct a self-shielding system with anisotropic interface distribution characteristics to generate competitive adsorption and peeling at the interface and simultaneously generate an in-situ passivation protective layer. Summary of the Invention

[0005] This invention provides a highly stable metal surface cleaning and degumming agent, comprising the following components:

[0006] Highly polar organic solvents with a mass percentage of 65% to 85%;

[0007] The perfluoroalkylsiloxane block copolymer has a mass percentage of 0.5% to 1.8%, wherein the perfluoroalkylsiloxane block copolymer is composed of perfluoroalkyl and siloxane segments, and the siloxane segments have active sites that bind to active hydroxyl groups on the surface of a metal substrate.

[0008] Organic amine auxiliaries with a mass percentage of 2% to 8%;

[0009] And replenish to 100% with a polar diluent, which is a polyol ether solvent that forms a hydrogen bond solvation shell with a highly polar organic solvent;

[0010] In this process, perfluoroalkylsiloxane block copolymers form microemulsion particles with a particle size of 80 nm to 150 nm in a polar diluent; at the gas-liquid interface of a highly stable metal surface cleaning degumming agent, the perfluoroalkylsiloxane block copolymers are oriented to form an interfacial barrier layer with a thickness of 5 nm to 20 nm and a surface tension lower than that of the highly polar organic solvent, thereby inhibiting the high polar organic solvent from reaching a concentration of 60 nm. Up to 80 Mass evaporation loss under operating conditions and prevention of environmental moisture penetration into the bulk phase of the high-stability metal surface cleaning and degumming agent; at the liquid-solid interface where the high-stability metal surface cleaning and degumming agent contacts the metal substrate, the perfluoroalkylsiloxane block copolymer occupies active hydroxyl sites on the surface of the metal substrate through active sites to form a displacement adsorption layer that replaces the cured adhesive layer on the surface of the metal substrate.

[0011] Preferably, the perfluoroalkyl group is... to The degree of polymerization of the perfluorolinear alkyl siloxane segments ranges from 15 to 45; the molecular weight distribution index of the perfluoroalkyl siloxane block copolymers is... Not greater than 1.25, and the perfluoroalkyl siloxane block copolymer connects the perfluoroalkyl and siloxane segments through urethane linkages; the interfacial barrier layer is at 80°C. The surface tension is maintained between 15 mN / m and 19 mN / m; the siloxane bonds in the siloxane segments combine with the active sites and active hydroxyl sites through hydrogen bonding, so that the interfacial adsorption energy of the perfluoroalkylsiloxane block copolymer on the metal substrate surface is greater than the adhesion energy of the cured adhesive layer on the metal substrate surface.

[0012] Preferably, the highly polar organic solvent is selected from at least one of N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, and dimethylacetamide; the organic amine auxiliaries are selected from at least one of monoethanolamine, triethanolamine, and tetramethylammonium hydroxide; and the deviation value of the Hansen solubility parameter between the highly polar organic solvent and the perfluoroalkylsiloxane block copolymer is... The concentration is kept within the range of 2.8 to 3.5 to maintain the dispersion stability of microemulsion particles in the bulk phase.

[0013] Preferably, the deviation value of Hansen's solubility parameter Determined according to the following formula: ,in, , , These represent the dispersion force, polarity, and hydrogen bonding parameters of highly polar organic solvents, respectively. , , These represent the dispersion force, polarity, and hydrogen bonding parameters of the perfluoroalkylsiloxane block copolymer, respectively.

[0014] Preferably, the distribution density of microemulsion particles in the polar diluent is: cells / mL to cells / mL; at 80 Under constant temperature and open conditions, after 120 hours of operation, the high-stability metal surface cleaning and degumming agent showed a mass loss rate of less than 3% for the highly polar organic solvent, and the mass percentage of water in the bulk phase remained below 0.5%.

[0015] Preferably, the organic amine additive severs the crosslinking points between the cured adhesive layer and the metal substrate surface through nucleophilic substitution, and works in conjunction with the displacement adsorption layer of the perfluoroalkylsiloxane block copolymer to completely peel the cured adhesive layer from the metal substrate surface.

[0016] Preferably, the polar diluent includes diethylene glycol monobutyl ether or triethylene glycol dimethyl ether; the polar diluent and the perfluoroalkylsiloxane block copolymer together construct a bicontinuous microemulsion structure in the bulk phase.

[0017] Preferably, the urethane linker adjusts the density of the perfluoroalkyl siloxane block copolymer in the interfacial barrier layer by changing the angle between the perfluoroalkyl and siloxane segments.

[0018] Preferably, the metal substrate is an aluminum alloy, copper foil, or copper-clad laminate; the adsorption work per unit area of ​​the perfluoroalkylsiloxane block copolymer at the liquid-solid interface is greater than the desorption work of the cured adhesive layer on the surface of the metal substrate.

[0019] Preferably, the material further includes a corrosion inhibitor at a mass percentage of 0.1% to 0.5%, wherein the corrosion inhibitor is benzotriazole or mercaptobenzothiazole, which is used together with the displacement adsorption layer to form a composite protective film to prevent microscopic electrochemical corrosion on the surface of the metal substrate.

[0020] Compared with existing technologies, the high-stability metal surface cleaning and degumming agent of this invention has the following advantages:

[0021] 1. In metal surface cleaning and degumming agents, the interface shielding-anchoring factor, leveraging the oleophobicity of perfluoroalkyl groups and the hydrophobicity of the siloxane backbone, is oriented and forms a dense barrier layer at the gas-liquid interface, effectively inhibiting the main solvent component from reaching 80°C. The evaporation rate under open working conditions is controlled, while preventing air moisture from penetrating into the bulk phase, maintaining the constant composition of the cleaning system, and ensuring long-term stable operation of the cleaning process window.

[0022] 2. Through the strong chemical anchoring force generated by the siloxane segments and the hydroxyl groups on the metal surface, the interface shielding-anchoring factor performs competitive displacement at the liquid-solid interface. The interface displacement energy forces the adhesive layer to desorb, transforming the traditional dissolution mode into an interface peeling mode, slowing down the viscosity rise rate of the bulk phase, and increasing the cumulative degumming load of a single bath solution. After the peeling action is completed, the interface shielding-anchoring factor forms a hydrophobic protective layer in situ on the newly exposed metal surface, increasing the electrochemical corrosion potential of the metal surface, blocking the secondary oxidation and micro-electrochemical corrosion of the activated metal surface by the atmospheric environment, and realizing the integrated function of cleaning and corrosion prevention.

[0023] 3. A metastable microemulsion system is constructed by combining low-volatility polar solvents with a specific amount of interfacial shielding-anchoring factor. The difference in solubility parameter drives the factor to exhibit a quasi-saturated migration state between the bulk phase and the interface, thereby enhancing interfacial activity without reducing the solvent swelling capacity and improving the engineering adaptability of the cleaning system under complex working conditions. Attached Figure Description

[0024] Figure 1 This is a diagram illustrating the interface shielding and displacement adsorption degumming mechanism of the high-stability cleaning degumming agent of this invention.

[0025] Figure 2 This is a flowchart of the closed-loop calibration process for the production parameters of a new batch of copolymers for solubility testing according to the present invention. Detailed Implementation

[0026] The technical solutions of the embodiments of this application will be clearly described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this application are within the scope of protection of this application.

[0027] It should be noted that all directional and positional terms used in this invention, such as: up, down, left, right, front, back, vertical, horizontal, inner, outer, top, low, lateral, longitudinal, center, etc., are only used to explain the relative positional relationship and connection between components in a specific state (as shown in the accompanying drawings). They are only for the convenience of describing this invention and do not require that this invention be constructed and operated in a specific orientation. Therefore, they should not be construed as limiting this invention. In addition, the descriptions of "first," "second," etc., in this invention are for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly indicating the number of technical features indicated.

[0028] In the description of this invention, unless otherwise explicitly specified and limited, the terms installation, connection, and linking should be interpreted broadly. For example, they can refer to fixed connections, detachable connections, or integral connections; they can refer to mechanical connections; they can refer to direct connections or indirect connections through an intermediate medium; they can refer to the internal communication between two components. For those skilled in the art, the specific meaning of the above terms in this invention can be understood according to the specific circumstances.

[0029] In the description of this specification, references to the terms "an embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example, and the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0030] The present invention will now be described in detail with reference to the embodiments thereof. The embodiments described below are intended to explain the present invention and are not intended to limit the scope of protection of the present invention.

[0031] This invention provides a highly stable metal surface cleaning and degumming agent, wherein the total mass of the degumming agent is... The calculation includes the percentage by mass. to Highly polar organic solvents, with a mass percentage of to Perfluoroalkylsiloxane block copolymers, with a mass percentage of to The organic amine auxiliaries and the balance polar diluent; the degumming agent is prepared from the above components through a specific shear emulsification process, forming a metastable microemulsion system with interfacial self-organization characteristics. The perfluoroalkylsiloxane block copolymer forms particles with a diameter of [missing information - likely a particle size] in the polar diluent. to Microemulsion particles migrate and arrange themselves at the gas-liquid and liquid-solid interfaces to maintain a constant bath composition and perform interfacial displacement degumming under high-temperature open conditions; in large-scale cleaning operations of precision aluminum alloys or copper-clad laminates, the cleaning solution is often in a state of... to In high-temperature, open-containment environments, highly polar organic solvents are prone to reduced cleaning efficiency due to volatilization and moisture absorption. Perfluoroalkylsiloxane block copolymers are introduced into the system as interfacial shielding and anchoring factors; the copolymers are composed of… to The perfluoro linear alkyl group is linked to a polyurethane segment with a degree of polymerization of to It is composed of siloxane segments linked together, and its molecular weight distribution index is... Not greater than The migration of perfluoroalkylsiloxane block copolymers to the interface is affected by the deviation of the Hansen solubility parameter between the highly polar organic solvent and the copolymer. drive, In to Within the interval, its calculation follows the formula: ,in, , , These represent the dispersion force parameter, polarity parameter, and hydrogen bonding parameter of highly polar organic solvents, respectively. , , These represent the dispersion force, polarity, and hydrogen bonding parameters of the perfluoroalkylsiloxane block copolymer, respectively; when Within this defined range, the perfluoroalkylsiloxane block copolymers are oriented at the gas-liquid interface of the degumming agent, forming a structure with a thickness of [missing information]. to Furthermore, the surface tension of the interfacial barrier layer is lower than that of highly polar organic solvents, and the interfacial barrier layer in... The surface tension below is to Within a certain range, it is used to block the evaporation path of solvent molecules and prevent environmental moisture from penetrating into the bulk phase.

[0032] Polar diluents are used in the system to adjust the hydrogen bond density of highly polar organic solvents and to assist in the microemulsification process of perfluoroalkylsiloxane block copolymers. When the mass percentage of the polar diluent is within a certain range... to Within a certain range, the thickness of the hydrogen-bonded solvated shell formed inside the system remains at [value missing]. to This thickness is sufficient to coat the siloxane segments in the copolymer and inhibit their excessive aggregation in the non-working state; if the polar diluent content is lower than If the swelling capacity of the system is too strong, the interfacial shielding layer cannot exist stably. If its content is higher than... This will reduce the dissolution rate of the cured adhesive layer. By locking the content of the polar diluent within the above range, the degumming agent can... The kinetic viscosity remains at to Between these points, ensure the penetration efficiency of the cleaning solution in the microscopic gaps of the metal; according to experimental measurements, in Operating under constant temperature and open conditions Afterwards, the mass loss rate of the highly polar organic solvent is less than And the water content in the bulk phase is maintained at The following measures ensure the stability of the cleaning process window under high-temperature and complex environments. Addressing the issue of high adhesion strength of cured adhesive layers on metal substrates, which makes peeling difficult, perfluoroalkylsiloxane block copolymers perform displacement adsorption at the liquid-solid interface. When the degumming agent contacts the surface of aluminum alloy, copper foil, or copper-clad laminate with cured adhesive layers, the siloxane segments in the copolymer bind to the active hydroxyl groups on the metal surface through their active sites. Because the interfacial adsorption energy is greater than the adhesion energy of the cured adhesive layer on the metal surface, the copolymer forcibly occupies the active hydroxyl sites and penetrates into the adhesive layer gaps, causing physical peeling of the adhesive layer. Simultaneously, organic amine additives, namely monoethanolamine, triethanolamine, or tetramethylammonium hydroxide, sever the crosslinking points between the cured adhesive layer and the metal substrate surface through affinity, synergistically desorbing the adhesive layer completely with the copolymer. The degumming method changes from overall dissolution to interfacial peeling, with the adhesive layer suspended or settled in fragmented form, avoiding a rapid increase in bulk viscosity due to polymer dissolution, thus increasing the cumulative degumming load per unit volume of degumming solution to the level of existing technologies. More than twice.

[0033] After the stripping process is completed, the perfluoroalkylsiloxane block copolymer molecular array remaining on the metal surface serves to construct a hydrophobic protective layer. This protective layer blocks the contact between the cleaned, activated metal surface and air moisture and oxygen, thereby increasing the electrochemical corrosion potential of the metal surface and shifting the corrosion potential to the positive direction. The above, along with the mass percentage content in the system, is... to The corrosion inhibitors, namely benzotriazole or mercaptobenzothiazole, work together to prevent secondary oxidation or pitting corrosion on the metal surface; the polar diluent, namely diethylene glycol monobutyl ether or triethylene glycol dimethyl ether, together with the perfluoroalkylsiloxane block copolymer in the bulk phase to construct a bicontinuous microemulsion structure, ensuring the uniform dispersion of each functional component in the system during long-term service; the preparation procedure of the high-stability metal surface cleaning and degumming agent is as follows: in a stirred tank with a temperature-controlled jacket, add a high-polarity organic solvent and a polar diluent according to a preset ratio, and... Stirring at high speed Minutes; Heat to Turn on the high-shear emulsifier and set the speed to [speed value missing]. The perfluoroalkylsiloxane block copolymer was added in four pulsed drops, with an interval between each drop. Within minutes, through high shear force, the copolymer forms particles with a size within a certain range in the polar solvent system. to Metastable microemulsion particles within the range; finally, organic amine additives and corrosion inhibitors are added, and stirring is maintained. The temperature is slowly reduced to room temperature at a rate of / min to complete the preparation of the finished product.

[0034] Perfluoroalkylsiloxane block copolymers are prepared by the addition reaction of hydroxyl-terminated polydimethylsiloxane with molecular weights of 1500 to 3500 and isocyanate-terminated perfluoroalkyl segments under the catalysis of dibutyltin dilaurate. The isocyanate index is controlled within the range of 1.02 to 1.05 to ensure complete conversion of the urethane bonds. The molar percentage of siloxane segments in the resulting product is limited to 65% to 75%, and the dispersion force parameters of the copolymer are locked. Polarity parameter and hydrogen bond term parameters , at 25 The initial values ​​calculated below satisfy the deviation values ​​from the Hansen solubility parameter for highly polar organic solvents. The requirement is that the thickness of the interfacial barrier layer, ranging from 5nm to 20nm, is monitored by an online dynamic surface tension meter to measure the gas-liquid interfacial tension. The rate of change over runtime is characterized when When the value deviates from the preset range of 15mN / m to 19mN / m, the system automatically fine-tunes the polar diluent feeding ratio based on the solvent composition fluctuations fed back by the online refractive index sensor, compensating for 80%. Solvent hydrogen bonding parameters caused by temperature under operating conditions Attenuation causes deviation in Hansen's solubility parameter value Stable within the 2.8 to 3.5 driving range, maintaining the continuity of the interfacial barrier layer and suppressing solvent molecule escape, the copolymer mass percentage is limited to the range of 0.5% to 1.8%. Below 0.5%, the molecular density at the gas-liquid interface is insufficient to form a dense monolayer with a coverage exceeding 95%, leading to a solvent evaporation rate more than three times the baseline value. Above 1.8%, the bulk phase forms microemulsion particles that undergo secondary aggregation, causing the degummed system to reach 80°C. When the kinetic viscosity exceeds 5.0 mPa·s, the resistance to solvent penetration into the microporous structure of the metal substrate is increased and the average degumming time is prolonged. By locking the content in this range, the cleaning efficiency and component steady-state synergy are achieved.

[0035] Example 1: In the application scenario of debonding aluminum alloy substrates for precision electronic modules, the debonding tank is in... In open-circulation operation, the high vapor pressure and hygroscopicity of highly polar organic solvents cause the bath solution mass to decrease with increasing running time. Furthermore, atmospheric moisture induces micro-pitting corrosion on the aluminum alloy surface, reducing the reliability of subsequent substrate encapsulation. The high-stability metal surface cleaning and degumming agent provided by this invention, wherein the mass percentage of perfluoroalkylsiloxane block copolymer is [missing information]. The highly polar organic solvent used is N-methylpyrrolidone. After the degumming agent is added to the circulation tank, its properties are determined based on the relationship between the perfluoroalkylsiloxane block copolymer and N-methylpyrrolidone. Hansen solubility parameter deviation value The driving copolymer forms a quasi-saturated distribution within the bulk phase and migrates towards the gas-liquid interface. During this process, low-energy perfluoroalkyl segments construct a thickness of [missing information] at the liquid surface. nm and surface tension is A molecular shielding layer with a density of mN / m.

[0036] This shielding layer reduces the diffusion rate of molecules at the liquid surface, allowing the solvent to... The evaporation rate is maintained at a preset low level, simultaneously preventing external water vapor from penetrating into the polar phase and maintaining the effective concentration of organic amine additives within the system. Meanwhile, at the interface between the aluminum alloy substrate and the cured adhesive layer, the siloxane segments of the copolymer, through their affinity for the active hydroxyl groups on the metal surface, perform competitive displacement adsorption, displacing the cured adhesive layer originally anchored to the substrate from the interface. This changes the adhesive layer desorption mode from dissolution to interfacial peeling. The cleaned aluminum alloy surface is covered by the generated perfluorinated molecular array, and its surface corrosion potential shifts positively. mV and without pitting marks, the system operates continuously After hours, the mass loss rate of the tank solution was controlled at... Within this process, the above process works synergistically through the shielding mechanism of perfluoroalkyl groups and the interfacial anchoring and displacement mechanism of siloxane segments. While solving the problem of solvent evaporation, it utilizes the difference in interfacial energy to reshape the stripping logic, allowing the cured adhesive layer to detach in a non-dissolving form. Under the premise of maintaining the stability of the bath solution, it increases the cumulative degumming load per unit volume of degumming liquid and uses the residual molecular array to establish a physical barrier on the metal surface to prevent secondary oxidation of the activated metal surface.

[0037] Example 2: Targeting highly polar organic solvents in To address the technical challenge of component imbalance caused by high vapor pressure and hygroscopicity under open-air conditions, a physical verification platform simulating an industrial cleaning environment was constructed, including a circulating heating jacket with a temperature control deviation of no more than [value missing]. A stainless steel cleaning tank, maintaining a flow rate above the liquid surface in the tank. An airflow of m / s was used to simulate an evaporation environment, with the relative humidity controlled at [value missing]. The experimental data was acquired using a real-time weighing system for the bath solution and a Karl Fischer moisture analyzer to obtain the moisture content of the degumming agent. The mass change rate and moisture content values ​​during continuous service cycles, and the logic behind setting the concentration of perfluoroalkylsiloxane block copolymers in the experiment, are based on their mass percentage content. It is necessary to balance the molecular arrangement density at the gas-liquid interface with the phase stability of the system. In to Within the specified range, the deviation value of Hansen solubility parameter between perfluoroalkylsiloxane block copolymers and highly polar organic solvents. Driven by this, molecules can form a dense shielding layer at the interface. When the concentration is below the lower limit of this range, the interface coverage is insufficient to block the escape kinetic energy of solvent molecules. If the concentration is above the upper limit of this range, the copolymer will generate particle aggregation in the bulk phase, leading to an increase in viscosity.

[0038] The experimental and control groups were constructed following the variable uniqueness criterion. The experimental group used a mass percentage of [missing information]. Perfluoroalkylsiloxane block copolymers, with a mass percentage of N-methylpyrrolidone and its mass percentage is The monoethanolamine, with the balance being diethylene glycol monobutyl ether; control group A had the perfluoroalkylsiloxane block copolymer removed, and control group B had the copolymer mass percentage set at [value missing]. The copolymer mass percentage of control group C was set as follows: In control group D, organic amine adjuvants were removed to verify the synergistic stripping mechanism; all sample groups were in Continuous operation under constant temperature open conditions h, during which the liquid surface in the tank is subjected to a flow velocity of The simulated airflow disturbance at m / s is shown in Table 1.

[0039] Table 1: Comparison of performance test results of degumming agents with different component configurations

[0040]

[0041] The test data in Table 1 show that the experimental group exhibits a definite technical advantage in maintaining constant solvent composition, with a mass loss rate of [missing data]. The performance inflection point data for control group B, which had its copolymer factor removed, showed that the concentration was lower than that of control group A. When the lower limit is reached, it is impossible to build a thickness of [amount missing] on the interface. A continuous barrier layer with a diameter greater than nm has a solvent mass loss rate of [missing information]. The high concentration cannot meet the requirements for long-term service; data from control group C show that when the concentration exceeds... After reaching the upper limit, although the effect of inhibiting volatilization was similar to that of the experimental group, the excessive formation of metastable microemulsion particles in the copolymer within the bulk phase increased the physical resistance to solvent penetration into the adhesive layer, resulting in a decrease in the average degumming time. s increased to The comparison between the control group D and the experimental group confirmed the synergistic effect between the perfluoroalkylsiloxane block copolymer and the organic amine additive. In the absence of the chemical cleavage effect of organic amine on the crosslinking points, relying solely on interfacial displacement peeling will lead to a decrease in degumming efficiency.

[0042] Example 3: This example combines Figures 1 to 2Description of a highly stable metal surface cleaning and degumming agent, such as... Figure 1 As shown, the mechanism of action of the highly stable metal surface cleaning and degumming agent begins with the original component system, which contains 65% to 85% by mass of a highly polar organic solvent, a perfluoroalkylsiloxane block copolymer, 2% to 8% by mass of an organic amine auxiliaries, and a polar diluent of polyol ethers. After dispersion and emulsification, the above components enter the microemulsion particle construction stage. At this time, the perfluoroalkylsiloxane block copolymer is distributed within the polar diluent, forming microemulsion particles with a particle size of 80 nm to 150 nm that are coated with a hydrogen-bonded solvated shell. These particles undergo directional migration and are oriented to form an interfacial barrier layer at the gas-liquid interface, with a thickness of 5 nm to 20 nm and a surface tension lower than that of the highly polar organic solvent. In this way, the interfacial shielding effect is achieved through functionality, i.e., inhibiting 60% of the surface tension of the solvent. Up to 80 Under operating conditions, the mass evaporation loss is blocked and the ambient moisture is blocked from penetrating into the bulk phase. At the same time, the microemulsion particles, through adsorption and binding, utilize the active sites of the copolymer to bind to the metal substrate and construct a displacement adsorption layer on the surface of the metal substrate. The mechanism is to occupy the active hydroxyl sites and then cause the cured adhesive layer to peel off through physical displacement. In this process, the cured adhesive layer on the metal surface is forcibly replaced and the bonds are broken with the assistance of organic amine additives.

[0043] like Figure 2 As shown, the parameter calibration process for a new batch of perfluoroalkylsiloxane block copolymers involves multiple interactive objects, including testing personnel, the new batch of copolymers, reference solvent groups, solubility testing, computing units, and the production system. Testing personnel select five reference solvents with known parameters and take samples, then proceed to the five reference solvent testing stage at 25... The equilibrium solubility test module transmits the recorded solubility data to the computing unit and performs a least squares nonlinear regression operation to calculate the dispersion force parameter, polarity parameter, and hydrogen bond parameter in sequence. Then, it calculates the deviation value of the Hansen solubility parameter. After inputting the above parameter data into the production system, the system corrects the chemical potential gradient of the feed and finally feeds back the information to the testing personnel that the calibration is complete and the system can be put into production.

[0044] Example 4: In a scenario where a debonding process is performed on an aluminum alloy precision packaging substrate with a high aspect ratio micro-blind via structure, the strong anchoring effect between the cured protective adhesive layer remaining on the inner wall of the micro-blind via and the metal surface, coupled with the micropores limiting the convection diffusion of the cleaning solution, leads to residue at the bottom of the via and induces pitting corrosion in the substrate during subsequent wet processing. Using the high-stability metal surface cleaning and debonding agent of this invention, parameter calibration is performed during the preparation stage based on the molecular characteristics of the highly polar organic solvent and the interface shielding factor. The highly polar organic solvent selected is N-methylpyrrolidone, and the mass percentage of the perfluoroalkylsiloxane block copolymer is set to [value missing]. The polar diluent used is triethylene glycol dimethyl ether. The system utilizes the Hansen solubility parameter deviation between perfluoroalkylsiloxane block copolymers and N-methylpyrrolidone. Driven molecules to migrate to the interface, when In to Within the range, a chemical potential gradient is generated inside the system pointing towards the interface, causing the hydrophobic perfluorinated segments to be arranged towards the liquid surface.

[0045] During the preparation process, a stirred tank with a temperature control jacket is used to heat the system to a certain temperature. And start the high-shear emulsifier and set the speed to [speed value missing]. The copolymer is introduced by generating transient mechanical energy at rpm to break the solvation shell and using a four-pulse dropping method, with each dropping interval being [missing information]. Within minutes, this feeding rhythm controls the instantaneous local supersaturation of the system to near the nucleation threshold. During the feeding intervals, molecular thermal motion completes the initial interfacial distribution, suppressing the Ostwald ripening effect between microdroplets and ensuring the stable particle size of the generated microemulsion particles. nm to In the nm range Determined according to the following formula: ,in, , , These represent the dispersion force, polarity, and hydrogen bonding parameters of highly polar organic solvents, respectively, with units of [missing information]. , , , These represent the dispersion force, polarity, and hydrogen bonding parameters of the perfluoroalkylsiloxane block copolymer, respectively, with units of [missing information]. .

[0046] When the degumming liquid enters When the constant temperature bath is applied to the precision aluminum alloy packaging substrate, the copolymer penetrates into the bottom of the micro-blind via along with the solvent. At the liquid-solid interface, the hydrogen bond energy levels between the siloxane segments and the active hydroxyl groups on the metal surface are at... kJ / mol to In the kJ / mol range, this energy level is higher than the non-covalent adhesion energy between the cured protective adhesive layer and the metal substrate. The copolymer performs displacement adsorption on the pore wall surface and forces the adhesive layer molecules to displace, while the perfluorinated segments form a layer above the liquid surface with a thickness of [missing information]. nm and surface tension is A dense shielding layer with a density of mN / m; during continuous system operation After hours, the change in moisture content within the system was monitored using a Karl Fischer moisture analyzer. for The change value is calculated according to the following formula: ,in, This represents the change in moisture content, expressed as a percentage by mass. This represents the percentage of water content by mass after the operation is completed. The initial water content is expressed as a percentage by mass; after cleaning, the inner walls of the micropores in the aluminum alloy are free of polymer residue, and the molecular protective layer formed on the surface increases the polarization resistance of the metal. times.

[0047] Example 5: Under the condition of parameter calibration for a new batch of perfluoroalkylsiloxane block copolymers, due to the fluctuation of monomer conversion rate during polymer synthesis affecting the copolymer block ratio, five reference solvents with known Hansen solubility parameters were selected and... The equilibrium solubility of perfluoroalkylsiloxane block copolymers in various reference solvents was determined. A nonlinear regression analysis was performed on the solubility data using the least squares method to determine the dispersion force parameters of this batch of copolymers. Polarity parameter and hydrogen bond term parameters ,in, The parameter for the dispersion force term is expressed in units of . , This is the polarity parameter, in units of , For hydrogen bond parameters, the unit is . The obtained values ​​are input into the processing unit of the production system and used to calculate the deviation value of Hansen's solubility parameter. The formula determines the interaction parameters between the current batch factor and the highly polar organic solvent, which are used to correct the feed chemical potential gradient during the preparation process.

[0048] When the system faces deployment environments where reactor specifications or stirring shear efficiency change, maintaining the microemulsion particle size generated by the pulsed dropping procedure within a certain range is crucial. nm to Within the nm range, perform on-site pre-commissioning procedures by installing a measurement accuracy of not less than [missing value] in the stirring tank circulation loop. NTU's online turbidity sensor monitors the transmittance of the system after adding organic amine additives, and determines the transmittance based on the desired level. And the turbidity fluctuation is in Less than within minutes The quantitative results of NTU serve as the basis for determining the completion of finished product preparation. This enables production devices of different specifications to achieve dynamic equilibrium of the internal phase state of the system through feedback adjustment, thus realizing the steady-state reproduction of the components of the highly stable metal surface cleaning degumming agent in different engineering sites.

[0049] Example 6: In containing In the deployment of an aluminum alloy degumming production line with a tank capacity of L and equipped with a high-frequency circulation filtration system, the continuous mechanical shear force generated by the cleaning pump and the loss carried out by the workpiece cause a shift in the equilibrium state of the microemulsion particles within the system. The system then executes online concentration compensation and phase maintenance procedures. The comprehensive refractive index of the tank solution is obtained in real time through an online refractive index sensor and turbidity monitoring unit installed in the circulation pipeline. In addition to transmittance characteristics, the dynamic mass percentage of perfluoroalkylsiloxane block copolymers in the current system was calculated using a pre-established correlation matrix between refractive index and component concentration. ,in, To measure the dynamic percentage concentration, when the monitoring results are obtained... Deviation from preset median The magnitude reached At that time, the production system calculates the pulse replenishment amount of the component according to the following formula. : ,in, To supplement the mass, the unit is... , This represents the total volume of the current tank solution, in units of... , Density of the degumming agent, in units of , The target mass percentage concentration, This is the yield constant for the supplementary factor.

[0050] When faced with intermittent process shutdowns and changes in solvent interfacial tension caused by temperature fluctuations, the system performs operations based on interfacial tension. The dynamic response logic utilizes an online surface tension meter for real-time monitoring. The instantaneous value, when Values ​​exceeding When a preset threshold is reached, an automatic fine-tuning command is triggered to adjust the ratio of the highly polar organic solvent to the perfluoroalkylsiloxane block copolymer, thereby maintaining the continuity of the molecular shielding layer at the gas-liquid interface. This method utilizes quantified physical parameter inputs to drive the particle size of the microemulsion formed by the perfluoroalkylsiloxane block copolymer during continuous operation. Stabilized after hours to Within the range, and the decrease in polarization resistance of the cleaned metal surface is not greater than .

[0051] The embodiments of this application have been described above with reference to the accompanying drawings. Unless otherwise specified, the embodiments and features in the embodiments of this application can be combined with each other. This application is not limited to the specific embodiments described above. The specific embodiments described above are merely illustrative and not restrictive. Those skilled in the art can make many other forms under the guidance of this application without departing from the spirit and scope of the claims, and all of these forms are within the protection scope of this application.

Claims

1. A highly stable metal surface cleaning and degumming agent, characterized in that, Includes the following components: Highly polar organic solvents with a mass percentage of 65% to 85%; The perfluoroalkylsiloxane block copolymer has a mass percentage of 0.5% to 1.8%, wherein the perfluoroalkylsiloxane block copolymer is composed of perfluoroalkyl and siloxane segments, and the siloxane segments have active sites that bind to active hydroxyl groups on the surface of a metal substrate. Organic amine auxiliaries with a mass percentage of 2% to 8%; And replenish to 100% with a polar diluent, which is a polyol ether solvent that forms a hydrogen bond solvation shell with a highly polar organic solvent; In this process, perfluoroalkylsiloxane block copolymers form microemulsion particles with a particle size of 80 nm to 150 nm in a polar diluent; at the gas-liquid interface of a highly stable metal surface cleaning degumming agent, the perfluoroalkylsiloxane block copolymers are oriented to form an interfacial barrier layer with a thickness of 5 nm to 20 nm and a surface tension lower than that of the highly polar organic solvent, thereby inhibiting the high polar organic solvent from reaching a concentration of 60 nm. Up to 80 Mass evaporation loss under operating conditions and prevention of environmental moisture penetration into the bulk phase of the high-stability metal surface cleaning and degumming agent; at the liquid-solid interface where the high-stability metal surface cleaning and degumming agent contacts the metal substrate, the perfluoroalkylsiloxane block copolymer occupies active hydroxyl sites on the surface of the metal substrate through active sites to form a displacement adsorption layer that replaces the cured adhesive layer on the surface of the metal substrate.

2. The high-stability metal surface cleaning and degumming agent according to claim 1, characterized in that, Perfluoroalkyl is to The degree of polymerization of the perfluorolinear alkyl siloxane segments ranges from 15 to 45; the molecular weight distribution index of the perfluoroalkyl siloxane block copolymers is... Not greater than 1.25, and the perfluoroalkyl siloxane block copolymer connects the perfluoroalkyl and siloxane segments through urethane linkages; the interfacial barrier layer is at 80°C. The surface tension is maintained between 15 mN / m and 19 mN / m; the siloxane bonds in the siloxane segments combine with the active sites and active hydroxyl sites through hydrogen bonding, so that the interfacial adsorption energy of the perfluoroalkylsiloxane block copolymer on the metal substrate surface is greater than the adhesion energy of the cured adhesive layer on the metal substrate surface.

3. The high-stability metal surface cleaning and degumming agent according to claim 1, characterized in that, The highly polar organic solvent is selected from at least one of N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, and dimethylacetamide; the organic amine auxiliaries are selected from at least one of monoethanolamine, triethanolamine, and tetramethylammonium hydroxide; the deviation value of the Hansen solubility parameter between the highly polar organic solvent and the perfluoroalkylsiloxane block copolymer. The concentration is kept within the range of 2.8 to 3.5 to maintain the dispersion stability of microemulsion particles in the bulk phase.

4. The high-stability metal surface cleaning and degumming agent according to claim 3, characterized in that, Hansen solubility parameter deviation value Determined according to the following formula: ,in, , , These represent the dispersion force, polarity, and hydrogen bonding parameters of highly polar organic solvents, respectively. , , These represent the dispersion force, polarity, and hydrogen bonding parameters of the perfluoroalkylsiloxane block copolymer, respectively.

5. The high-stability metal surface cleaning and degumming agent according to claim 1, characterized in that, The distribution density of microemulsion particles in the polar diluent is cells / mL to cells / mL; at 80 Under constant temperature and open conditions, after 120 hours of operation, the high-stability metal surface cleaning and degumming agent showed a mass loss rate of less than 3% for the highly polar organic solvent, and the mass percentage of water in the bulk phase remained below 0.5%.

6. The high-stability metal surface cleaning and degumming agent according to claim 1, characterized in that, Organic amine additives sever the crosslinking points between the cured adhesive layer and the metal substrate surface through nucleophilic substitution, and work synergistically with the displacement adsorption layer of the perfluoroalkylsiloxane block copolymer to completely peel the cured adhesive layer off the metal substrate surface.

7. The high-stability metal surface cleaning and degumming agent according to claim 1, characterized in that, The polar diluents include diethylene glycol monobutyl ether or triethylene glycol dimethyl ether; the polar diluents and perfluoroalkylsiloxane block copolymers together construct a bicontinuous microemulsion structure in the bulk phase.

8. The high-stability metal surface cleaning and degumming agent according to claim 2, characterized in that, The urethane linker adjusts the density of the perfluoroalkyl siloxane block copolymer in the interfacial barrier layer by changing the angle between the perfluoroalkyl and siloxane segments.

9. The high-stability metal surface cleaning and degumming agent according to claim 1, characterized in that, The metal substrate is aluminum alloy, copper foil, or copper-clad laminate; the adsorption work per unit area of ​​the perfluoroalkylsiloxane block copolymer at the liquid-solid interface is greater than the desorption work of the cured adhesive layer on the surface of the metal substrate.

10. A highly stable metal surface cleaning and degumming agent according to claim 1, characterized in that, It also includes a corrosion inhibitor at a mass percentage of 0.1% to 0.5%, which is benzotriazole or mercaptobenzothiazole, used together with the displacement adsorption layer to form a composite protective film to prevent micro-electrochemical corrosion on the surface of the metal substrate.

Images