A resistive conductive material, its preparation method and use
By introducing a dispersed reinforcing phase and a transition layer into the resistive material, the problems of low resistivity and poor etch resistance are solved, resulting in a resistive material with high resistivity and good etch resistance, suitable for the manufacture of printed circuit boards.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- JIUJIANG TELFORD ELECTRONICS MATERIAL CO LTD
- Filing Date
- 2025-01-14
- Publication Date
- 2026-06-16
AI Technical Summary
Existing resistive materials have low resistivity and are not resistant to chemical etching, resulting in insufficient stability and reliability of embedded resistive devices during the manufacturing process.
The structure consists of a copper foil layer, a transition layer, and a resistive layer. The resistive layer contains a dispersed reinforcing phase and a homogeneous phase, which are prepared by electroplating. The dispersed reinforcing phase is distributed in the resistive layer in the form of particles or clusters, which increases the resistivity and improves the etching resistance.
A resistive material with a resistivity higher than 3×10-3Ω·cm has been achieved, which has excellent etching resistance, ensuring that the resistive layer is not damaged during the etching process and maintaining the stability and reliability of the resistive device.
Smart Images
Figure CN120076170B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of electronic materials technology, and specifically relates to a resistive conductive material, its preparation method, and its application. Background Technology
[0002] With the rapid development of the electronics and information industry, printed circuit boards (PCBs) are developing towards high density, multi-layer, easy packaging, and miniaturization. Considering the reliability of PCB assembly, the stability of resistors, and electrical performance, the embedding of resistors is essential. The emergence of embedded copper foil has solved this problem very well.
[0003] Currently, commercially available buried resistive copper foil is typically fabricated by electroplating or vacuum sputtering, where a layer of resistive material is deposited onto a copper foil substrate. These resistive materials include binary, ternary, and even quaternary metal alloys. Because these alloys all contain metallic components, their resistivity is generally low, typically less than 1 × 10⁻⁶. -3 Ω·cm. Power load per unit area (unit: W / in). 2 Both electrostatic discharge (ESD) capability and sheet resistance (R) are related to the resistivity of the material. □ Under certain circumstances, according to R □ =ρ / d, the larger the resistivity ρ, the larger the size d of the resistor, and the stronger the power load and ESD of the resistor.
[0004] In the manufacturing process of buried resistor PCBs, continuous chemical etching is required to obtain the resistor pattern, and the sheet resistance R of the resistor layer is determined. □ Etching is inevitable. Adding a barrier layer between the copper foil and the resistive layer can effectively protect the resistive layer from etching. However, the resistivity of the alloy material used in the resistive layer is already low, and the resistivity of the barrier layer is even lower. Adding a barrier layer will further reduce the resistivity. Therefore, to obtain stable embedded resistor devices, the problems of low resistivity and poor resistance to chemical etching of existing resistive materials must be solved. Summary of the Invention
[0005] The technical problem to be solved by the present invention is to provide a resistive conductive material, its preparation method and application, which not only has a very high resistivity (greater than 3 × 10⁻⁶), but also has a very high resistivity (greater than 3 × 10⁻⁶). -3 It has an Ω·cm content and exhibits excellent resistance to etching solutions.
[0006] The present invention provides a resistive conductive material, which comprises, from bottom to top, a copper foil layer, a transition layer and a resistive layer; the resistive layer comprises a dispersed reinforcing phase and a homogeneous phase; the dispersed reinforcing phase undergoes surface pretreatment before being added to the electroplating solution.
[0007] Preferably, the transition layer contains one or more elements selected from tin, nickel, zinc, chromium, oxygen, phosphorus, carbon, nitrogen, aluminum, titanium, silicon, and cobalt, and contains at least one metallic element.
[0008] Preferably, the thickness of the transition layer is 5-30 nm.
[0009] Preferably, the ratio of the surface roughness Ra of the transition layer on the side closest to the copper foil layer to the thickness of the transition layer is between 30 and 600.
[0010] Preferably, the thickness of the resistive layer is 0.05-1 μm. The resistive layer and the copper foil layer are electrically conductive.
[0011] Preferably, the dispersed reinforcing phase is a metal oxide, a non-metal oxide, or a ferrite; the homogeneous phase is a nickel-phosphorus alloy.
[0012] Furthermore, the mass m1 of the dispersed reinforcing phase accounts for 15%-35% of the total mass m2 of the resistive layer, and the fluctuation of the ratio does not exceed ±10%.
[0013] Furthermore, the phosphorus content in the nickel-phosphorus alloy is greater than 12 wt%.
[0014] Preferably, the dispersed reinforcing phase includes one or more of the following: silicon dioxide, boron oxide, zinc oxide, magnesium oxide, bismuth oxide, aluminum oxide, titanium dioxide, nickel oxide, tungsten oxide, cobalt oxide, copper oxide, chromium oxide, manganese oxide, zirconium oxide, zinc ferrite, magnetic iron oxide, nickel zinc ferrite, and copper zinc ferrite.
[0015] Furthermore, the resistive layer has metal clusters distributed on the side of its surface away from the transition layer, and the metal clusters are composed of nickel and phosphorus.
[0016] Furthermore, on the side of the resistive layer away from the transition layer, there is no dispersed reinforcing phase distribution within a depth of 15 nm from the surface; the dispersed reinforcing phase is distributed in the homogeneous phase in the form of particles or clusters.
[0017] Furthermore, the surface roughness Ra of the resistive layer on the side away from the transition layer is between 1.0 and 3.0 μm, and the Sdr is between 50% and 300%.
[0018] The present invention also provides a method for preparing a resistive conductive material, comprising the following steps:
[0019] S1. Prepare copper foil layer;
[0020] S2. Prepare a transition layer on the copper foil layer;
[0021] S3. The electroplating solution used to prepare the resistive layer;
[0022] S4. Electroplating is performed on the transition layer using the above-mentioned electroplating solution to obtain a resistive conductive material.
[0023] Furthermore, in step S1, existing copper foil production technology is used to prepare the copper foil layer. The existing production technology includes electrolysis and rolling, and the nominal thickness of the final copper foil layer is between 5-200 μm.
[0024] Furthermore, in step S2, a transition layer is prepared on the copper foil layer by chemical or physical methods. Chemical methods include electroplating, electroless plating, chemical vapor deposition, etc., while physical methods include vacuum evaporation, ion plating, magnetron sputtering, etc.
[0025] Further, the electroplating solution in step S3 comprises a nickel source, a phosphorus source, a stabilizer, a buffer, a pH adjuster, an additive, and a dispersion reinforcing phase. Specifically, the nickel source, calculated by nickel atom concentration, is 15-50 g / L; the phosphorus source, calculated by phosphorus atom concentration, is 8-15 g / L; the stabilizer concentration is 0.1-5 g / L; the buffer concentration is 10-100 g / L; the additive concentration is 0.05-2 g / L; the dispersion reinforcing phase concentration is 0.3-1 g / L; and the pH adjuster concentration can be dynamically adjusted according to the actual pH change of the electroplating solution, with the final pH of the electroplating solution being 1.5-3.
[0026] Furthermore, the nickel source includes one or more of nickel sulfamate, nickel sulfate, nickel chloride, and nickel carbonate; the phosphorus source includes one or more of sodium hypophosphite, phosphorous acid, and hypophosphite; the stabilizer includes one or more of thiourea, sodium acetate, sodium thiosulfate, potassium iodide, ethylenediaminetetraacetic acid, and methyltetrahydrophthalic anhydride; the buffer includes one or more of boric acid, phosphoric acid, citric acid, lactic acid, malic acid, and tartaric acid; the pH adjuster includes one or more of sulfuric acid, ammonia, sodium hydroxide, and potassium hydroxide; and the additives include one or more of sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium 2-ethylhexyl sulfate, polyethylene glycol, sodium tungstate, and saccharin.
[0027] Furthermore, the particle size D of the dispersed reinforcing phase 90 Between 30-90nm, D 50 Between 15-48nm, the specific surface area is between 50-300m². 2 / g.
[0028] Furthermore, the added dispersion-enhancing phase is pretreated using a mixed solution of polyol and water as a solvent and a surfactant as a treatment agent.
[0029] Further, the polyol comprises one or more of ethylene glycol, glycerol, diethylene glycol, pentaerythritol, butanediol, triethanolamine, xylitol, sorbitol, and neopentyl glycol; the surfactant comprises one or more of CTAB, cationic polyacrylamide, hexadecylpyridinium chloride, hexadecyltrimethylammonium chloride, vinylpyrrolidone, tetradecyl-dimethylpyridinium bromide, epichlorohydrin and ethylenediamine condensate, dimethyl diallyl ammonium chloride, and diethylaminoethyl acrylate; wherein the polyol accounts for more than 50% of the mass of the alcohol-water mixed solution.
[0030] Further, 1-10g of the dispersion-enhancing phase is added to a mixed solution of polyol and water and ultrasonically stirred for 0.5-2h; then the surfactant is added to the mixed solution and ultrasonically stirred for another 1-5h, with the solution temperature maintained at 30-60℃, and the weight ratio of the dispersion-enhancing phase to the surfactant being 1:5-1:15.
[0031] Furthermore, after the dispersion-enhanced phase has undergone surface pretreatment, it is separated using a high-speed centrifuge, washed sequentially with ethanol and water, and finally vacuum dried at a temperature of 80°C.
[0032] Furthermore, the treated dispersed reinforcing phase is added to the electroplating solution, and air is introduced into the solution to ensure thorough dispersion of the components. The air flow rate is 0.5-5 m³ / h. 3 / min.
[0033] Further, the electroplating in step S4 is as follows: using DSA titanium material as the anode, and copper foil as the cathode opposite the anode, wherein the copper foil is fixed on an insulating substrate, the electroplating solution temperature is 30-60℃, and the current density is 0.5-20A / dm³. 2 The electroplating method is pulse electroplating with a duty cycle of 30%-100%.
[0034] This invention also provides an application of resistive conductive materials in the preparation of copper-clad laminates, comprising the following steps:
[0035] S5. The resistive conductive material is laminated with a prepreg (PP) to obtain copper clad laminate (FCCL);
[0036] S6. Etch and perform performance testing on the laminated FCCL.
[0037] Furthermore, before pressing in step S5, the obtained resistive conductive material is washed clean with water, dried with hot air at 80°C, and then the resistive layer side is pressed with the prepreg.
[0038] Furthermore, the semi-cured sheet includes epoxy resin-based PP, hydrocarbon resin-based PP, PTFE resin-based PP, PPO / PPE resin-based PP, bismaleimide (BMI) and polymaleimide resin-based PP, LCP liquid crystal polymer, cyanate ester resin-based PP, ABF resin-based PP, phenolic resin-based PP, etc.
[0039] Furthermore, in step S6, the pressed resistive conductive material is etched, the copper foil layer and the transition layer are completely etched and dissolved, and the remaining resistive layer is tightly attached to the cured PP board.
[0040] Furthermore, the etching solution is preferably an alkaline copper ammonia etching solution.
[0041] Furthermore, in step S6, an XRF thickness gauge is used to measure the thickness of the resistive layer, a sheet resistance meter is used to test the sheet resistance of the resistive layer, and the resistivity of the resistive layer is calculated.
[0042] Furthermore, in step S6, the sheet resistance of the resistive layer is tested at different etching times to obtain the etch resistance of the resistive layer.
[0043] Beneficial effects
[0044] This invention adds a dispersed reinforcing phase to the resistive layer. This phase, with nanoscale dimensions, is distributed in the homogeneous nickel-phosphorus phase as particles or clusters, acting as anchoring points, inhibiting the diffusion of defects in the homogeneous phase, cutting off the etchant's intrusion path into the resistive layer, and improving the resistive layer's etching resistance. Furthermore, the dispersed reinforcing phase is an insulator and non-conductive, hindering electron transport, extending the electron transport path, and increasing the resistivity of the resistive layer. Secondly, while the copper foil layer readily undergoes diffusion reactions with the resistive layer, the introduction of the transition layer and the dispersed reinforcing phase, working synergistically, inhibits the diffusion of copper into the resistive layer, maintaining its high resistivity, and demonstrating promising application prospects. Attached Figure Description
[0045] Figure 1 This is a schematic diagram of the resistive conductive material structure of the present invention;
[0046] Figure 2 This is a partially enlarged schematic diagram of the resistive conductive material structure of the present invention;
[0047] Figure 3 This is a schematic diagram of the resistive conductive material structure after lamination.
[0048] Figure 4 This is a schematic diagram of the resistive conductive material structure after etching. Detailed Implementation
[0049] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.
[0050] Example 1
[0051] Step S1:
[0052] Copper foil is obtained by electrolysis and then surface-treated. The nominal thickness of the copper foil is 18 μm.
[0053] Step S2:
[0054] A nickel-tin alloy is electroplated on the rough surface of the copper foil as a transition layer, wherein the mass fraction of tin is 60%, the total thickness of the transition layer is 15 nm, and the roughness Ra = 0.9 μm.
[0055] Step S3:
[0056] 1) First, prepare the pretreatment solution of the dispersion-enhancing phase by mixing ethylene glycol, diethylene glycol and water to obtain a polyol aqueous solution. The total mass is calculated based on 100 parts by mass. The mass ratio of the three components is 40:15:45. Stir well and set aside for use.
[0057] 2) Secondly, 1g of nickel oxide was used as the dispersed reinforcing phase, with a particle size D. 90 =80nm, D 50 =42nm, specific surface area 235m² 2 / g, add to the above polyol aqueous solution, and ultrasonically stir for 1h;
[0058] 3) Add 5g of CTAB to the above polyol solution, continue ultrasonic stirring for 2 hours, and maintain the temperature at 30℃ in a water bath.
[0059] 4) Separate nickel oxide by centrifugation, wash it with ethanol and deionized water in turn, and dry it in a vacuum drying oven at 80°C for 2 hours;
[0060] 5) Prepare a nickel-phosphorus electroplating solution. The nickel source is nickel sulfate, the phosphorus source is phosphorous acid, the stabilizer is thiourea, the buffer is phosphoric acid, and the additive is sodium dodecyl sulfate. Use sulfuric acid and sodium hydroxide to adjust the pH of the solution. The specific concentrations are: nickel sulfate 120 g / L, phosphorous acid 25 g / L, thiourea 0.2 g / L, phosphoric acid 40 g / L, sodium dodecyl sulfate 0.05 g / L, and the pH of the solution is 2.0.
[0061] 6) Add the dried nickel oxide to the nickel-phosphorus electroplating solution at a rate of 0.6 g / L, and introduce air while stirring. The air flow rate is 0.5 m3 / min to obtain the electroplating solution.
[0062] Step S4:
[0063] Using DSA titanium as the anode and copper foil as the cathode, with the copper foil fixed on an insulating substrate, the electroplating bath temperature was 30℃ and the current density was 0.5A / dm³. 2 A pulsed current was applied for 20 minutes with a duty cycle of 90% to obtain a resistive conductive material. The surface roughness of the resistive layer on the side away from the transition layer was Ra = 1.05 μm and sdr = 55%.
[0064] Step S5:
[0065] The obtained resistive conductive material was removed from the substrate, washed with water, dried at 80°C, and then its resistive layer was pressed tightly against the FR4 prepreg at a pressing temperature of 200°C for 3 hours.
[0066] Step S6:
[0067] The laminated resistive conductive material is placed horizontally on the sample stage. The copper foil layer and transition layer of the resistive conductive material are horizontally etched using a multi-point spray method. The horizontal movement speed of the sample stage is 5 m / min. After etching, the resistive layer is fully exposed. The thickness of the resistive layer is measured, and the sheet resistance of the resistive layer at different etching times is tested.
[0068] Example 2
[0069] Unlike Example 1, in step S3, an equal weight of tungsten oxide is used as the dispersed reinforcing phase, and the particle size D 90 =85nm, D 50 =40nm, specific surface area 220m² 2 / g.
[0070] Example 3
[0071] Unlike Example 1, in step S3, an equal weight of titanium dioxide is used as the dispersed reinforcing phase, and the particle size D 90 =90nm, D 50 =48nm, specific surface area 215m² 2 / g.
[0072] Example 4
[0073] Unlike Example 1, in step S3, an equal weight of silicon dioxide is used as the dispersed reinforcing phase, and the particle size D 90 =40nm, D 50 =25nm, specific surface area 290m²2 / g.
[0074] Example 5
[0075] Unlike Example 1, in step S3, an equal weight of bismuth oxide is used as the dispersed reinforcing phase, and the particle size D 90 =78nm, D 50 =36nm, specific surface area 250m² 2 / g.
[0076] Example 6
[0077] Unlike Example 1, in step S3, an equal weight of zinc ferrite was used as the dispersed reinforcing phase, and the particle size D 90 =86nm, D 50 =40nm, specific surface area 186m² 2 / g.
[0078] Example 7
[0079] Unlike Example 1, in step S3, a pretreatment solution for the dispersion-enhancing phase is prepared. The polyols used are ethylene glycol, sorbitol, and water, with a mass ratio of 35:20:45. Other conditions are the same as in Example 1.
[0080] Example 8
[0081] Unlike Example 1, in step S3, the surfactant is vinylpyrrolidone.
[0082] Example 9
[0083] Unlike Example 1, in step S2, a nickel-carbon alloy is used as a transition layer on the rough surface of the copper foil, wherein the mass fraction of nickel is 92%, the total thickness of the transition layer is 15 nm, and the roughness Ra = 0.88 μm.
[0084] Comparative Example 1
[0085] Unlike Example 1, no dispersion-enhancing phase is added in step S3.
[0086] Comparative Example 2
[0087] Unlike Example 1, in step S3, after the dispersion-enhancing phase is fully dispersed in the alcohol-water mixture, no surfactant is used to perform subsequent surface treatment on the dispersion-enhancing phase.
[0088] Comparative Example 3
[0089] Unlike Example 1, in step S3, the mass ratio of the three components ethylene glycol, diethylene glycol, and water is 30:15:55, while other conditions are the same as in Example 1.
[0090] Comparative Example 4
[0091] Unlike Example 1, in step S3, the electroplating conditions are: electroplating solution temperature 30°C, current density 0.5 A / dm³. 2 The pulse is applied for 20 minutes with a duty cycle of 25%.
[0092] Comparative Example 5
[0093] Unlike Example 1, this resistive conductive material does not have a transition layer.
[0094] To more intuitively illustrate the effects of the present invention, all embodiments and comparative examples used the same pressing, etching, and testing procedures (steps S5 and S6). Specific test data are shown in Table 1.
[0095]
[0096]
[0097] To more clearly highlight the beneficial effects of the present invention, the embodiments and comparative examples are described in detail below.
[0098] Comparing Comparative Example 1 with Example 1, without the addition of a dispersed reinforcing phase to the resistive layer, the resistivity is extremely low, only 0.5 × 10⁻⁶. -3 The resistivity was measured in Ω·cm, and the rate of change in resistivity within 12 minutes was 540%, indicating highly unstable resistivity. Such a resistive conductive material has no practical application value. Comparing Example 2 with Example 1, without using surfactants to surface-treat the dispersed reinforcing phase, the dispersed reinforcing phase in the resistive layer was only 7.8% by mass, and the resistivity of the resistive layer was only 1.5 × 10⁻⁶ Ω·cm. -3 The resistivity change rate reached 113% in Ω·cm, indicating instability. Compared to Example 1, Comparative Example 3 showed a polyol mass ratio below 50%, resulting in insufficient dispersion of the dispersed reinforcing phase and affecting the final resistivity. Compared to Example 1, Comparative Example 4 reduced the duty cycle, decreased the resistive layer thickness, and lowered the doping amount of the dispersed reinforcing phase to 10% by mass, resulting in a resistivity reduction to 1.8 × 10⁻⁶. -3 Ω·cm. Compared with Example 1, Comparative Example 5 had no transition layer, and the rate of change in resistivity increased from 10.4% to 20%, which is due to the diffusion of copper elements from the copper foil layer into the resistive layer.
[0099] Comparing Examples 2, 3, and 5 with Example 1, it can be seen that replacing nickel oxide with other substances, such as tungsten oxide, titanium dioxide, or bismuth oxide, can also improve resistivity. Comparing Example 4 with Example 1, its dispersed reinforcing phase has the largest specific surface area, which is beneficial for the dispersion of the dispersed reinforcing phase in the electroplating solution, thereby increasing its proportion in the resistive layer, and achieving a maximum resistivity of 5.3 × 10⁻⁶. -3 Ω·cm. Comparing Example 6 with Example 1, zinc ferrite has a smaller specific surface area, which is not conducive to dispersion in the plating bath, resulting in the lowest resistivity among all examples. Comparing Example 7 with Example 1, sorbitol was used instead of diethylene glycol, and the ratio was adjusted, achieving the same effect of increasing resistivity, with a better rate of resistivity change. Comparing Example 8 with Example 1, vinylpyrrolidone was used instead of CTAB, with good results. Comparing Example 9 with Example 1, the composition of the transition layer was changed, resulting in a slight increase in resistivity; at an etching time of 12 min, the resistivity change rate decreased to 7.69%.
[0100] Note that the above are merely preferred embodiments and the technical principles applied in this invention. Those skilled in the art will understand that the embodiments of this invention are not limited to the specific embodiments described herein, and various obvious changes, readjustments, and substitutions can be made without departing from the protection scope of this invention. Therefore, although the embodiments of this invention have been described in detail above, the embodiments of this invention are not limited to the above embodiments. More other equivalent embodiments may be included without departing from the concept of the embodiments of this invention, and the scope of the embodiments of this invention is determined by the scope of the appended claims.
Claims
1. A resistive conductive material, characterized in that: The resistive conductive material comprises, from bottom to top, a copper foil layer, a transition layer, and a resistive layer; the resistive layer comprises a dispersed reinforcing phase and a homogeneous phase; the dispersed reinforcing phase undergoes surface pretreatment before being added to the electroplating solution; the specific steps of the surface pretreatment are as follows: 1-10g of the dispersed reinforcing phase is added to a mixed solution of polyol and water, and ultrasonically stirred for 0.5-2h; then, a surfactant is added to the mixed solution, and ultrasonic stirring continues for 1-5h, with the solution temperature maintained at 30-60℃, and the weight ratio of the dispersed reinforcing phase to the surfactant is 1:5-1:15; the polyol comprises one or more of ethylene glycol, glycerol, diethylene glycol, pentaerythritol, butanediol, triethanolamine, xylitol, sorbitol, and neopentyl glycol; wherein the polyol accounts for more than 50% of the mass of the alcohol-water mixed solution.
2. The resistive conductive material according to claim 1, characterized in that: The transition layer contains one or more elements selected from tin, nickel, zinc, chromium, oxygen, phosphorus, carbon, nitrogen, aluminum, titanium, silicon, and cobalt, and contains at least one metallic element; the thickness of the transition layer is 5-30 nm; the thickness of the resistive layer is 0.05-1 μm.
3. The resistive conductive material according to claim 1, characterized in that: The dispersed reinforcing phase is a metal oxide, a non-metal oxide, or a ferrite; the homogeneous phase is a nickel-phosphorus alloy.
4. The resistive conductive material according to claim 1 or 3, characterized in that: The dispersed reinforcing phase includes one or more of the following: silicon dioxide, boron oxide, zinc oxide, magnesium oxide, bismuth oxide, aluminum oxide, titanium dioxide, nickel oxide, tungsten oxide, cobalt oxide, copper oxide, chromium oxide, manganese oxide, zirconium oxide, zinc ferrite, magnetic iron oxide, nickel zinc ferrite, and copper zinc ferrite.
5. The resistive conductive material according to claim 1, characterized in that: Metal clusters are distributed on the side of the resistive layer away from the transition layer.
6. A method for preparing the resistive conductive material as described in claim 1, comprising the following steps: S1. Prepare a copper foil layer; S2. Prepare a transition layer on the copper foil layer; S3. The electroplating solution used to prepare the resistive layer; S4. Electroplating is performed on the transition layer using the above-mentioned electroplating solution to obtain a resistive conductive material.
7. The preparation method according to claim 6, characterized in that: The electroplating solution in step S3 consists of a nickel source, a phosphorus source, a stabilizer, a buffer, a pH adjuster, additives, and a dispersion-enhancing phase.
8. The preparation method according to claim 7, characterized in that: The nickel source includes one or more of nickel sulfamate, nickel sulfate, nickel chloride, and nickel carbonate; the phosphorus source includes one or more of sodium hypophosphite, phosphorous acid, and hypophosphite; the stabilizer includes one or more of thiourea, sodium acetate, sodium thiosulfate, potassium iodide, ethylenediaminetetraacetic acid, and methyltetrahydrophthalic anhydride; the buffer includes one or more of boric acid, phosphoric acid, citric acid, lactic acid, malic acid, and tartaric acid; the pH adjuster includes one or more of sulfuric acid, ammonia, sodium hydroxide, and potassium hydroxide; and the additives include one or more of sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium 2-ethylhexyl sulfate, polyethylene glycol, sodium tungstate, and saccharin.
9. The application of the resistive conductive material as described in claim 1 in the preparation of copper-clad laminates.