Protective adhesive tape for electroplating process and preparation method of protective adhesive tape

Abstract

The invention discloses a protective adhesive tape for an electroplating process and a preparation method thereof, and relates to the technical field of surface treatment.The protective adhesive tape comprises a release layer, a first adhesive layer, a barrier layer, a second adhesive layer and a base material layer which are sequentially stacked, and all the layers form an integrated structure through hot-pressing compounding. A three-dimensional mutual transmission network is formed through fluorinated graphene and nano silicon dioxide, microdefects of a glue layer can be filled up, the density of a barrier layer can be improved through the used fluorine-doped aluminum oxide coating, interlayer gaps can be eliminated through the vacuum ultrasonic composite technology, and the bonding strength of the barrier layer is improved. Therefore, the obtained protective adhesive tape for the electroplating process has high shielding property and anti-permeation effect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of surface treatment, in particular to a protective tape for electroplating process and a preparation method thereof. BACKGROUND

[0002] In the electroplating process, it is often necessary to selectively protect the specific parts of the workpiece to avoid non-target areas from being electroplated.

[0003] The existing protective tape for electroplating process has the following defects:

[0004] 1. Patent document JP2000129452A discloses electroplating protective paint, electroplating layer and its production laminate, but the device in the above document has microscopic defects and interlayer voids, which leads to poor shielding performance and cannot effectively block the penetration of electroplating solution.

[0005] 2. Patent document JPH1060317A discloses a non-electroplating corrosion protection method and a non-electroplating protective paint composition, but the device in the above document has limited resistance to strong acidic electroplating solution and is easily corroded and damaged.

[0006] 3. Patent document JP2016032082A discloses a protective method for electroplating film, assembly and light emitting device, but the device in the above document has difficulty in balancing initial flexible fitting and long-term rigid support, leading to poor initial fitting or poor stability after long-term use, and the peeling resistance is prone to produce residual glue.

[0007] 4. Patent document CN118048603B discloses a conductive carbon coating anode for electroplating copper process and its preparation method and application, but the device in the above document has the technical problem that under high temperature electroplating process conditions, the glue layer or the substrate is prone to thermal softening, creep or shear deformation, leading to displacement, warping or sealing failure of the tape. SUMMARY

[0008] The present application aims to provide a protective tape for electroplating process and a preparation method thereof to solve the technical problems raised in the background.

[0009] To achieve the above-mentioned purpose, the present application provides the following technical solution: a protective tape for electroplating process and a preparation method thereof, comprising a release layer, a first glue layer, a barrier layer, a second glue layer and a substrate layer stacked in turn, and each layer is formed into an integrated structure by hot pressing.

[0010] The thickness of the release layer is 20-30 μm, which is composed of fluorinated polyethylene terephthalate.

[0011] The first adhesive layer has a thickness of 5-10 μm and comprises the following components by weight:

[0012] 55-65 parts of hydroxyl-terminated polydimethylsiloxane;

[0013] 0.1-0.5 parts of surface-modified fluorinated graphene, which has a layer number of ≤5, a lateral size of 1-5 μm, and a surface grafting rate of 8-15 wt% of γ-aminopropyl triethoxysilane;

[0014] 5-10 parts of nanoscale fumed silica, which has a particle size of 10-30 nm;

[0015] 0.3-0.8 parts of platinum-gold catalyst;

[0016] The barrier layer has a thickness of 40-60 μm and is composed of an aluminum foil with a 50-500 nm fluorine-doped aluminum oxide coating and a polyethylene terephthalate composite film, wherein the aluminum foil has a thickness of 10-14 μm, the polyethylene terephthalate composite film has a thickness of 30-46 μm, and the fluorine atom doping amount is 0.5-1.2 at%;

[0017] The second adhesive layer has a thickness of 12-18 μm and comprises the following components by weight:

[0018] 65-75 parts of hydrogenated nitrile rubber;

[0019] 2-4 parts of hollow polyphenyl ester microspheres loaded with hindered phenol antioxidant, which have a particle size of 0.5-2 μm, a wall thickness of ≤100 nm, an antioxidant loading amount of 20-30 wt%, and a polytetrafluoroethylene core;

[0020] 3-7 parts of zinc oxide whiskers;

[0021] 1.0-2.0 parts of peroxide crosslinking agent;

[0022] The substrate layer has a thickness of 80-120 μm and is composed of a glass fiber-reinforced polytetrafluoroethylene film modified by plasma grafting, and the plasma treatment power is 200-400 W.

[0023] Preferably, the mass ratio of the fluorinated graphene to the nanoscale fumed silica is 1:15-25, and the two form a three-dimensional interpenetrating network structure in the hydroxyl-terminated polydimethylsiloxane.

[0024] Preferably, the hollow polyphenyl ester microspheres have a compressive strength of ≥15 MPa and a volume expansion rate of ≤1.5% after being immersed in an electrolyte with pH=1 for 120 h.

[0025] Preferably, the working steps of the electroplating process protective tape are as follows:

[0026] S1, barrier layer processing: composite aluminum foil with polyethylene terephthalate composite film, magnetron sputtering aluminum oxide coating in argon and hexafluoropropylene mixed atmosphere, forming fluorine-doped aluminum oxide coating;

[0027] S2, adhesive layer preparation:

[0028] First adhesive layer: surface modified fluorinated graphene, nanoscale fumed silica and hydroxyl-terminated polydimethylsiloxane are pre-dispersed in a three-roll mill, then platinum catalyst is added;

[0029] Second adhesive layer: hollow polystyrene microspheres loaded with antioxidants are mixed with hydrogenated nitrile rubber in a supercritical CO2 environment;

[0030] S3, vacuum lamination: under a vacuum environment of ≤10 -2 Pa, axial ultrasonic vibration is applied to the substrate layer, and each layer is laminated;

[0031] S4, electron beam crosslinking: gradient dose irradiation is used, the first stage is 10kGy, and the second stage is 20kGy.

[0032] Preferably, the substrate temperature of the magnetron sputtering in S1 is controlled at 80-100℃, the sputtering rate is 0.5-1nm / s, and the ratio of hexafluoropropylene to argon is 1:50-100.

[0033] Preferably, the viscosity of the first adhesive layer after pre-dispersion in S2 is controlled at 30000-40000cps at room temperature 25℃, and the curing condition is curing at 150℃ for 90s.

[0034] Preferably, the roll gap of the three-roll mill in the first adhesive layer of S2 is ≤10μm, and the temperature is 60-80℃.

[0035] Preferably, the mixing pressure in the second adhesive layer of S2 is 18-22MPa, the temperature is 50-60℃, and the time is ≥30min.

[0036] Preferably, the axial ultrasonic vibration frequency in S3 is 20-40kHz, and the amplitude is 5-10μm.

[0037] Preferably, the beam current density in the first stage of S4 is 2mA / cm 2 , and the beam current density in the second stage is 5mA / cm 2 .

[0038] Compared with the prior art, the beneficial effects of the present application are:

[0039] 1. The present application can fill the micro defects of the adhesive layer by forming a three-dimensional inter-transmission network with fluorinated graphene and nano silicon dioxide, the fluorine-doped aluminum oxide coating used can improve the density of the barrier layer, and the use of vacuum ultrasonic compounding process can eliminate interlayer voids, thereby enabling the obtained electroplating process protective tape to have strong shielding and anti-permeation effects;

[0040] 2. The present application can improve the acid resistance by using fluorine-doped aluminum oxide coating, and hollow polystyrene microspheres can inhibit the penetration of electrolyte, and the substrate layer is modified by plasma grafting to provide the body corrosion resistance, thereby enabling the obtained electroplating process protective tape to have extremely good chemical corrosion resistance;

[0041] 3. The present application adopts the design of "soft and hard combination" of double adhesive layers, wherein the first adhesive layer is flexible to ensure the initial adhesion, and the second adhesive layer is rigid to provide long-term stability, and the lubricating effect of the fluorinated graphene used can reduce the peeling resistance, thereby enabling the obtained electroplating process protective tape to achieve precise peeling and reduce the residual amount;

[0042] 4. The present application can improve the high temperature deformation resistance of the protective tape by plasma treatment, nano fumed silica forming a thermally stable skeleton and the interlayer slip effect of the multi-layer fluorinated graphene inhibiting high temperature shear deformation, thereby meeting the high temperature electroplating process requirements. BRIEF DESCRIPTION OF DRAWINGS

[0043] Figure 1 It is a structure diagram of the electroplating process protective tape of the present application.

[0044] In the figure: 1, release layer; 2, first adhesive layer; 3, barrier layer; 4, second adhesive layer; 5, substrate layer. DETAILED DESCRIPTION

[0045] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0046] Example 1: Please refer to Figure 1 The present application provides an embodiment: a protective tape for electroplating process and a preparation method thereof, comprising a release layer 1, a first adhesive layer 2, a barrier layer 3, a second adhesive layer 4 and a substrate layer 5 which are stacked in sequence, and each layer is formed into an integrated structure by hot pressing compounding;

[0047] The thickness of the release layer 1 is 25 μm, which is composed of fluorinated polyethylene terephthalate;

[0048] The first adhesive layer 2 has a thickness of 8 μm and comprises the following components by weight:

[0049] 60 parts of hydroxyl-terminated polydimethylsiloxane;

[0050] 0.3 parts of surface-modified fluorinated graphene with 3 layers, lateral size of 3 μm and surface grafting rate of 12 wt% of γ-aminopropyl triethoxysilane;

[0051] 8 parts of nano-sized fumed silica with particle size of 20 nm;

[0052] 0.5 parts of platinum-gold catalyst;

[0053] The barrier layer 3 has a thickness of 50 μm and is an aluminum foil-polyethylene terephthalate composite film with a 200 nm fluorine-doped aluminum oxide coating on the surface, wherein the doping amount of fluorine atoms is 0.8 at%;

[0054] The second adhesive layer 4 has a thickness of 15 μm and comprises the following components by weight:

[0055] 70 parts of hydrogenated nitrile rubber;

[0056] 3 parts of hollow polyphenyl ester microspheres loaded with hindered phenol antioxidant with particle size of 1 μm, wall thickness of 80 nm, antioxidant loading amount of 25 wt%, and inner core of polytetrafluoroethylene;

[0057] 5 parts of zinc oxide whiskers;

[0058] 1.5 parts of peroxide crosslinking agent;

[0059] The substrate layer 5 has a thickness of 100 μm and is composed of a glass fiber-reinforced polytetrafluoroethylene film modified by plasma grafting, with a plasma treatment power of 300 W;

[0060] The working steps of the electroplating process protective tape are as follows:

[0061] S1, barrier layer 3 treatment: 12 μm aluminum foil is combined with 38 μm polyethylene terephthalate, and an aluminum oxide coating is formed by magnetron sputtering in an argon and hexafluoropropylene mixed atmosphere, with a ratio of argon to hexafluoropropylene of 75:1, a substrate temperature of 90°C, and a sputtering rate of 0.8 nm / s;

[0062] S2, adhesive layer preparation:

[0063] The first adhesive layer 2: the surface modified fluorinated graphene, nanoscale fumed silica and hydroxyl-terminated polydimethylsiloxane are pre-dispersed in a three-roll mill, the pre-dispersed viscosity of the first adhesive layer 2 is controlled at 35000 cps at room temperature 25℃, the curing condition is 150℃ for 90s, wherein the roll gap of the three-roll mill is 8μm, the dimension is 70℃, and a platinum catalyst is further added;

[0064] The second adhesive layer 4: the hollow polystyrene microspheres loaded with antioxidants and hydrogenated nitrile rubber are mixed in a supercritical CO2 environment, the mixing pressure in the second adhesive layer 4 is 20MPa, the temperature is 55℃, and the time is 40min;

[0065] S3, vacuum compounding: under the vacuum environment of 10 -3 Pa, axial ultrasonic vibration is applied to the substrate layer 5 to laminate each layer, wherein the frequency of the axial ultrasonic vibration is 30kHz, and the amplitude is 8μm;

[0066] S4, electron beam crosslinking: gradient dose irradiation is adopted, the first stage is 10kGy, the beam current density is 2mA / cm 2 , the second stage is 20kGy, and the beam current density is 5mA / cm 2 .

[0067] Example 2: please refer to Figure 1 , the present application provides an embodiment: a protective tape for electroplating process and a preparation method thereof, which comprises a release layer 1, a first adhesive layer 2, a barrier layer 3, a second adhesive layer 4 and a substrate layer 5 which are sequentially laminated, and each layer is integrated by hot pressing compounding;

[0068] The thickness of the release layer 1 is 25μm, which is composed of fluorinated polyethylene terephthalate;

[0069] The thickness of the first adhesive layer 2 is 8μm, which comprises the following components by weight:

[0070] Hydroxyl-terminated polydimethylsiloxane 60 parts;

[0071] Surface modified fluorinated graphene 0.1 parts, 3 layers, lateral size 3μm, surface grafting rate 12wt% of γ-aminopropyl triethoxysilane;

[0072] Nanoscale fumed silica 10 parts, particle size 20nm;

[0073] Platinum catalyst 0.5 parts;

[0074] The thickness of the barrier layer 3 is 50μm, which is an aluminum foil-polyethylene terephthalate composite film with a 50nm fluorine-doped aluminum oxide coating on the surface, wherein the doping amount of fluorine atoms is 0.5at%;

[0075] The second adhesive layer 4 has a thickness of 15 μm and comprises the following components by weight:

[0076] 70 parts of hydrogenated nitrile rubber;

[0077] 2 parts of hollow polyphenyl ester microspheres loaded with hindered phenol antioxidant, with a particle size of 1 μm, a wall thickness of 80 nm, an antioxidant loading of 25 wt%, and a polytetrafluoroethylene core;

[0078] 5 parts of zinc oxide whiskers;

[0079] 1.5 parts of peroxide crosslinking agent;

[0080] The substrate layer 5 has a thickness of 100 μm and is composed of a glass fiber reinforced polytetrafluoroethylene film modified by plasma grafting, with a plasma treatment power of 200 W;

[0081] The working steps of the electroplating process protective tape are as follows:

[0082] S1, barrier layer 3 treatment: 12 μm aluminum foil is combined with 38 μm polyethylene terephthalate, and an aluminum oxide coating is formed by magnetron sputtering in an argon and hexafluoropropylene mixed atmosphere, with a ratio of argon to hexafluoropropylene of 75:1, a substrate temperature of 90°C, and a sputtering rate of 0.8 nm / s;

[0083] S2, adhesive layer preparation:

[0084] First adhesive layer 2: surface-modified fluorinated graphene, nanoscale fumed silica, and hydroxyl-terminated polydimethylsiloxane are pre-dispersed in a three-roll mill, with the pre-dispersed viscosity of the first adhesive layer 2 controlled at 35,000 cps at room temperature of 25°C, and the curing conditions being 150°C for 90 seconds, wherein the roll gap of the three-roll mill is 8 μm, and the dimension is 70°C, and a platinum catalyst is then added;

[0085] Second adhesive layer 4: antioxidant-loaded hollow polyphenyl ester microspheres are mixed with hydrogenated nitrile rubber in a supercritical CO2 environment, with a mixing pressure of 16 MPa, a temperature of 55°C, and a time of 40 minutes in the second adhesive layer 4;

[0086] S3, vacuum lamination: under a vacuum environment of 10 -3 Pa, axial ultrasonic vibration is applied to the substrate layer 5 to laminate the layers, wherein the frequency of the axial ultrasonic vibration is 30 kHz, and the amplitude is 8 μm;

[0087] S4, electron beam crosslinking: gradient dose irradiation is used, with 10 kGy in the first stage and a beam current density of 2 mA / cm 2 , and 20 kGy in the second stage and a beam current density of 5 mA / cm 2 .

[0088] Embodiment 3: please refer to Figure 1 In one embodiment, the present application provides a protective tape for electroplating process and a preparation method thereof, which comprises a release layer 1, a first adhesive layer 2, a barrier layer 3, a second adhesive layer 4 and a substrate layer 5 which are sequentially stacked and integrated by hot pressing.

[0089] The thickness of the release layer 1 is 25 μm, which is composed of fluorinated polyethylene terephthalate;

[0090] The thickness of the first adhesive layer 2 is 8 μm, which comprises the following components by weight:

[0091] Hydroxyl-terminated polydimethylsiloxane 60 parts;

[0092] Surface-modified fluorinated graphene 0.5 parts, 3 layers, lateral size 3 μm, surface grafting rate of γ-aminopropyl triethoxysilane 12 wt%;

[0093] Nanoscale fumed silica 5 parts, particle size 20 nm;

[0094] Platinum gold catalyst 0.5 parts;

[0095] The thickness of the barrier layer 3 is 50 μm, which is an aluminum foil-polyethylene terephthalate composite film with a 500 nm fluorine-doped aluminum oxide coating on the surface, wherein the fluorine atom doping amount is 1.2 at%;

[0096] The thickness of the second adhesive layer 4 is 15 μm, which comprises the following components by weight:

[0097] Hydrogenated nitrile rubber 70 parts;

[0098] Hollow polyphenyl ester microspheres loaded with hindered phenolic antioxidant 4 parts, particle size 1 μm, wall thickness 80 nm, antioxidant loading 30 wt%, inner core polytetrafluoroethylene;

[0099] Zinc oxide whiskers 5 parts;

[0100] Peroxide crosslinking agent 1.5 parts;

[0101] The thickness of the substrate layer 5 is 100 μm, which is composed of a glass fiber reinforced polytetrafluoroethylene film modified by plasma grafting, and the plasma treatment power is 400 W;

[0102] The working steps of the electroplating process protective tape are as follows:

[0103] S1, barrier layer 3 treatment: 12 μm aluminum foil is combined with 38 μm polyethylene terephthalate, and an aluminum oxide coating is formed by magnetron sputtering in an argon and hexafluoropropylene mixed atmosphere, the ratio of argon to hexafluoropropylene is 75:1, the substrate temperature is 90℃, and the sputtering rate is 0.8 nm / s;

[0104] S2, adhesive layer preparation:

[0105] First adhesive layer 2: surface-modified fluorinated graphene, nanoscale fumed silica and hydroxyl-terminated polydimethylsiloxane are pre-dispersed in a three-roll mill. The pre-dispersed viscosity of the first adhesive layer 2 is controlled at 35,000 cps at room temperature 25°C. The curing condition is 150°C for 90s, wherein the roll gap of the three-roll mill is 8μm, the dimension is 70°C, and a platinum catalyst is further added.

[0106] Second adhesive layer 4: antioxidant-loaded hollow polystyrene microspheres and hydrogenated nitrile rubber are mixed in a supercritical CO2 environment. The mixing pressure in the second adhesive layer 4 is 20MPa, the temperature is 55°C, and the time is 40min.

[0107] S3, vacuum lamination: under a vacuum environment of 10 -3 Pa, axial ultrasonic vibration is applied to the substrate layer 5, and the layers are laminated, wherein the frequency of the axial ultrasonic vibration is 30kHz, and the amplitude is 8μm.

[0108] S4, electron beam crosslinking: gradient dose irradiation is used, the first stage is 10kGy, the beam current density is 2mA / cm 2 , the second stage is 20kGy, and the beam current density is 5mA / cm 2 .

[0109] Comparative Example 1: An embodiment provided by the present application: prepared by the method of Example 1, which is different from Example 1 in that no surface-modified fluorinated graphene is added, and other raw materials, steps and parameters are the same as Example 1.

[0110] Comparative Example 2: An embodiment provided by the present application: prepared by the method of Example 1, which is different from Example 1 in that the barrier layer 3 uses a pure aluminum oxide coating without doping fluorine, and other raw materials, steps and parameters are the same as Example 1.

[0111] Comparative Example 3: An embodiment provided by the present application: prepared by the method of Example 1, which is different from Example 1 in that the second adhesive layer 4 has no hollow polystyrene microspheres, and other raw materials, steps and parameters are the same as Example 1.

[0112] Comparative Example 4: An embodiment provided by the present application: prepared by the method of Example 1, which is different from Example 1 in that S3 does not use ultrasonic vibration, and other raw materials, steps and parameters are the same as Example 1.

[0113] Comparative Example 5: An embodiment provided by the present application: ordinary PE film is used.

[0114] Performance test:

[0115] Test 1: Edge Penetration Test: The protective tapes obtained in Examples 1-3 and Comparative Examples 1-5 were cut into 50mm x 100mm strips, applied to the edge of a standard electroplating steel plate (100mm x 100mm x 1mm), ensuring that 1mm of the tape overhung the edge, and then immersed in a nickel plating solution at 80±2°C, pH=1.0±0.1, under a pressure of 0.2MPa, for a test time of 120h. After removal, the samples were disassembled and the maximum depth of penetration of the plating solution was measured using a laser confocal microscope.

[0116] Test 2: Swelling Rate Test: The protective tapes obtained in Examples 1-3 and Comparative Examples 1-5 were cut into 20mm x 20mm square samples, immersed in a nickel plating solution at 80±1°C, pH=1.0, for 120h, and after immersion the surface weight was wiped dry and the surface topography was scanned.

[0117] Test 3: Peeling Residue Test: The protective tapes obtained in Examples 1-3 and Comparative Examples 1-5 were cut into 20mm x 20mm square samples, applied to a standard electroplating steel plate (100mm x 100mm x 1mm), and after being placed in an oven at 150°C for 30min, the samples were subjected to a peeling test in a testing machine. Finally, the surface of the steel plate was wiped with acetone and the percentage of residual area was calculated using image analysis software.

[0118] Test 4: High Temperature Resistance Test: The protective tapes obtained in Examples 1-3 and Comparative Examples 1-5 were cut into 20mm x 20mm square samples, placed in a high temperature test chamber, and the high temperature deformation temperature of the samples was tested.

[0119] Table 1 Performance tests of protective tapes for electroplating processes

[0120]

[0121] Further, by forming a three-dimensional mutual transmission network with fluorinated graphene and nanosilica, the micro defects of the adhesive layer can be filled. The fluorine-doped aluminum oxide coating used can improve the density of the barrier layer 3, and the use of a vacuum ultrasonic compounding process can eliminate interlayer voids, thereby enabling the obtained protective tape for electroplating processes to have strong shielding and anti-permeation effects.

[0122] The use of a fluorine-doped aluminum oxide coating helps to improve acid resistance, and hollow polystyrene microspheres can inhibit the penetration of electrolyte. Further graft modification of the substrate layer 5 using plasma provides bulk corrosion resistance, thereby enabling the obtained protective tape for electroplating processes to have excellent chemical corrosion resistance.

[0123] Through the design of the "soft and hard combination" of the double adhesive layers, the first adhesive layer 2 is flexibly attached to ensure the initial attachment, the second adhesive layer 4 is rigidly supported to provide long-term stability, and the lubricating effect of the fluorinated graphene used can reduce the peeling resistance, thereby enabling the protective adhesive tape obtained by the electroplating process to achieve precise peeling and reduce the residual amount;

[0124] Through the plasma treatment, the formation of the thermal stable skeleton by nano fumed silica and the interlayer slip effect of the multi-layer fluorinated graphene, high temperature shear deformation is inhibited, thereby the effect of improving the high temperature deformation resistance of the protective adhesive tape can be improved, and the high temperature electroplating process demand can be met.

[0125] The protective adhesive tape of the present application is suitable for selective electroplating processing of high-end products such as automotive electroplated parts and bathroom hardware, and can significantly improve the product yield.

[0126] The working principle is that a three-dimensional mutual transmission network is formed by fluorinated graphene and nano silica dioxide, which can fill the micro defects of the adhesive layer, the fluorine-doped aluminum oxide coating used can improve the density of the barrier layer 3, and the interlayer voids can be eliminated by using a vacuum ultrasonic composite process, thereby the protective adhesive tape obtained by the electroplating process has strong shielding and anti-permeation effects, the use of fluorine-doped aluminum oxide coating helps to improve the acid resistance, hollow polystyrene microspheres can inhibit the penetration of electrolyte, and the substrate layer 5 is grafted and modified by plasma, providing the body corrosion resistance, thereby the protective adhesive tape obtained by the electroplating process has excellent chemical corrosion resistance, through the design of the "soft and hard combination" of the double adhesive layers, the first adhesive layer 2 is flexibly attached to ensure the initial attachment, the second adhesive layer 4 is rigidly supported to provide long-term stability, and the lubricating effect of the fluorinated graphene used can reduce the peeling resistance, thereby enabling the protective adhesive tape obtained by the electroplating process to achieve precise peeling and reduce the residual amount, through the plasma treatment, the formation of the thermal stable skeleton by nano fumed silica and the interlayer slip effect of the multi-layer fluorinated graphene, high temperature shear deformation is inhibited, thereby the effect of improving the high temperature deformation resistance of the protective adhesive tape can be improved, and the high temperature electroplating process demand can be met, the protective adhesive tape of the present application is suitable for selective electroplating processing of high-end products such as automotive electroplated parts and bathroom hardware, and can significantly improve the product yield.

[0127] It is apparent to those skilled in the art that the present application is not limited to the details of the foregoing exemplary embodiments, but can be implemented in other specific forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be considered in all respects as illustrative and not restrictive, the scope of the present application being defined by the appended claims rather than by the foregoing description, and it is intended that all changes which come within the meaning and range of equivalency of the claims are resolvable position the present application. Any reference signs in the claims should not be construed as limiting the claims to the figures in which the reference signs are used.

Claims

1. A protective tape for use in an electroplating process, characterized by: The protective tape comprises a release layer (1), a first adhesive layer (2), a barrier layer (3), a second adhesive layer (4) and a substrate layer (5) which are sequentially stacked and are integrated by hot pressing. The release layer (1) has a thickness of 20-30 microns and is made of fluorinated polyethylene terephthalate. The first adhesive layer (2) has a thickness of 5-10 microns and comprises the following components by weight: hydroxyl-terminated polydimethylsiloxane 55-65 parts; surface-modified fluorinated graphene 0.1-0.5 parts, which has a layer number of less than 5, a lateral size of 1-5 microns and a surface grafting rate of 8-15 wt% of γ-aminopropyl triethoxysilane; nanoscale fumed silica 5-10 parts, which has a particle size of 10-30 nm; platinum-gold catalyst 0.3-0.8 parts; The barrier layer (3) has a thickness of 40-60 microns and is made of an aluminum foil with a fluorine-doped aluminum oxide coating layer having a thickness of 50-500 nm and a polyethylene terephthalate composite film, wherein the aluminum foil has a thickness of 10-14 microns and the polyethylene terephthalate composite film has a thickness of 30-46 microns, and the fluorine atom doping amount is 0.5-1.2 at%. The second adhesive layer (4) has a thickness of 12-18 microns and comprises the following components by weight: hydrogenated nitrile rubber 65-75 parts; hollow polyphenyl ester microspheres loaded with a hindered phenol antioxidant 2-4 parts, which have a particle size of 0.5-2 microns, a wall thickness of less than 100 nm and an antioxidant loading amount of 20-30 wt%, and an inner core of polytetrafluoroethylene; zinc oxide whiskers 3-7 parts; peroxide crosslinking agent 1.0-2.0 parts; The substrate layer (5) has a thickness of 80-120 microns and is made of a glass fiber-reinforced polytetrafluoroethylene film modified by plasma grafting, and the plasma treatment power is 200-400 W.

2. A protective tape for use in an electroplating process according to claim 1, characterized in that: The mass ratio of the fluorinated graphene to the nanoscale fumed silica is 1:15-25, and the two form a three-dimensional interpenetrating network structure in the hydroxyl-terminated polydimethylsiloxane.

3. The protective tape for use in an electroplating process according to claim 1, wherein: The hollow polyphenyl ester microspheres have a compressive strength of greater than or equal to 15 MPa and a volume expansion rate of less than or equal to 1.5% after being immersed in an electrolyte with a pH of 1 for 120 hours.

4. A method of manufacturing a protective tape for electroplating processes according to any one of claims 1-3, characterized in that, The working steps of the electroplating process protective tape are as follows: S1, barrier layer (3) treatment: composite the aluminum foil and the polyethylene terephthalate composite film, magnetron sputter an aluminum oxide coating layer in an argon and hexafluoropropylene mixed atmosphere to form a fluorine-doped aluminum oxide coating layer; S2, adhesive layer preparation: first adhesive layer (2): pre-disperse the surface-modified fluorinated graphene, nanoscale fumed silica and hydroxyl-terminated polydimethylsiloxane in a three-roll mill, and then add the platinum-gold catalyst; second adhesive layer (4): mix the hollow polyphenyl ester microspheres loaded with an antioxidant and the hydrogenated nitrile rubber in a supercritical CO2 environment; S3, vacuum compounding: in ≤10 -2 under a vacuum environment, applying axial ultrasonic vibration to the substrate layer (5) to laminate each layer; S4, electron beam crosslinking: use gradient dose irradiation, 10 kGy in the first stage and 20 kGy in the second stage.

5. The method for preparing a protective tape for electroplating processes according to claim 1, characterized in that: In S1, the substrate temperature of magnetron sputtering is controlled at 80-100℃, the sputtering rate is 0.5-1 nm / s, and the ratio of hexafluoropropylene to argon is 1:50-100.

6. The method for preparing a protective tape for electroplating processes according to claim 1, characterized in that: The pre-dispersed viscosity of the first adhesive layer (2) in S2 is controlled at 30000-40000 cps at normal temperature 25℃, and the curing condition is 150℃ for 90s.

7. The method for preparing a protective tape for electroplating processes according to claim 1, characterized in that: The roll gap of the three-roll grinder in the first adhesive layer (2) in S2 is ≤10μm, and the temperature is 60-80℃.

8. The method for preparing a protective tape for electroplating processes according to claim 1, characterized in that: The mixing pressure in the second adhesive layer (4) in S2 is 18-22MPa, the temperature is 50-60℃, and the time is ≥30min.

9. A method for preparing a protective tape for electroplating processes according to claim 1, characterized in that: The axial ultrasonic vibration frequency in S3 is 20-40kHz, and the amplitude is 5-10μm.

10. A method for preparing a protective tape for electroplating processes according to claim 1, characterized in that: The first stage of the beam current density in S4 is 2 mA / cm 2 , and the second stage of the beam current density is 5 mA / cm 2 .

Images