Copper sulfate ointment, copper sulfate ointment patch, and preparation method and application of copper sulfate ointment patch

Abstract

The invention belongs to the technical field of plant pesticides and chemical products, and discloses a copper sulfate ointment, a copper sulfate ointment patch and a preparation method and application of the copper sulfate ointment patch, and the copper sulfate ointment comprises the following components in parts by mass: 1-10 parts of copper sulfate, 40-50 parts of a thickening agent, 2-8 parts of a humectant and 30-50 parts of water serving as a solvent. The preparation method of the copper sulfate paste comprises the following steps: S1, putting the thickening agent into a proper amount of distilled water, heating and stirring to completely dissolve the thickening agent to form a uniform glue solution; s2, adding copper sulfate powder into the glue solution until the copper sulfate powder is uniformly dispersed in the glue solution; s3, a humectant is added, and copper sulfate paste is prepared; and molding the copper sulfate paste. The copper sulfate paste is simple in formula, combines the chemical characteristics of copper sulfate and the physical advantages of a paste preparation, is convenient to use, efficient in slow release, lasting in effect, capable of achieving precise application, capable of reducing medicine waste, improved in safety, diversified in application scene and convenient to store and transport.

Description

Technical Field

[0001] This invention relates to the field of plant pesticides and chemical products, and in particular to a copper sulfate ointment, a copper sulfate ointment patch, and a method for preparing the same. Background Technology

[0002] Copper sulfate is highly effective in controlling plant fungi, inhibiting or killing a variety of fungi. Even at low concentrations, it directly prevents the germination of plant pathogen spores and the growth of mycelia, thus reducing the source of infection. Pathogens are unlikely to develop resistance to copper sulfate, making it widely used in agriculture, horticulture, and industrial preservation.

[0003] However, copper sulfate powder has significant limitations in application, storage, and transportation: on the one hand, it is easily dispersed, making it unsafe to use, and it readily absorbs moisture and clumps; on the other hand, copper sulfate solution is inconvenient to transport and store, and prone to leakage. Currently, in agricultural applications, copper sulfate is either directly applied or mixed with lime to create Bordeaux mixture. However, neither of these preparations is resistant to rain washout and lacks a slow-release effect, resulting in low utilization efficiency of copper sulfate and difficulty in achieving the desired control effect.

[0004] In addition, when copper sulfate is washed into the soil by rainwater, copper ions cause serious soil pollution and have a significant impact on the soil microbial community.

[0005] Currently, there is a lack of copper sulfate preparations that are simple to prepare, have good sustained-release effects, and are easy to store and use. Therefore, existing technologies need further improvement. Summary of the Invention

[0006] To address the aforementioned problems, this invention provides a copper sulfate paste that is simple to prepare, can stably store copper sulfate, and can slowly and continuously release copper sulfate according to actual needs in practical use. The invention also provides a method for preparing the copper sulfate paste and its application.

[0007] To solve the above-mentioned technical problems, this application provides the following technical solution: In a first aspect, this application provides a copper sulfate paste comprising the following components in parts by weight: 1-10 parts copper sulfate, 40-50 parts thickener, and 2-8 parts humectant, with water as the solvent (30-50 parts water).

[0008] Optionally, in the copper sulfate paste, the thickener is gum arabic.

[0009] Preferably, in the copper sulfate paste, the mass ratio of gum arabic to water is 0.8 to 1.2.

[0010] Preferably, the humectant is glycerin. During the preparation process, 100% glycerin or an aqueous solution of glycerin may be added to achieve a final concentration of 2-8% in the copper sulfate ointment.

[0011] In the copper sulfate ointment, copper sulfate serves as the active ingredient, providing copper ions with bactericidal activity. Gum arabic is selected as the thickener to adjust the consistency of the ointment, ensuring suitable spreadability and a slow-release effect. Glycerin is selected as the humectant to prevent the ointment from drying out and to maintain its softness and stability.

[0012] Secondly, this application also provides a copper sulfate ointment patch, which includes a carrier material and the aforementioned copper sulfate ointment uniformly coated on the surface of the carrier.

[0013] Optionally, the copper sulfate plaster patch may contain a flexible material that can absorb or adhere to the copper sulfate plaster; alternatively, the carrier material may be gauze or non-woven fabric.

[0014] Thirdly, this application also provides a method for preparing the above-mentioned copper sulfate paste, which includes the following steps: S1. Dissolving the thickener: Place the corresponding amount of thickener into an appropriate amount of distilled water and soak at room temperature for 8-12 hours to allow the thickener to fully absorb water and swell; then heat and stir to completely dissolve the thickener and form a uniform and transparent gel; the heating temperature is 60~70℃. S2. Dissolving copper sulfate: Slowly add copper sulfate powder to the adhesive solution prepared in the previous step, while heating and stirring, until the copper sulfate powder is evenly dispersed in the adhesive solution; the heating temperature is 60~70℃; optionally, if the solution is found to be too thick and difficult to stir, an appropriate amount of distilled water can be added to adjust the viscosity.

[0015] S3. Addition of humectant: Add a humectant with a final concentration of 2-8% (mass percentage) to the mixture and continue stirring until homogeneous to prepare copper sulfate paste; S4. Forming of copper sulfate paste: Pour the copper sulfate paste with adjusted viscosity into a mold to form a shape that is easy to use; or the copper sulfate paste can be directly applied to a carrier material to prepare a copper sulfate plaster.

[0016] Finally, pack the prepared ointment with moisture-proof packaging material to prevent it from absorbing too much moisture and dissolving prematurely during storage.

[0017] The optimal heating temperature for gum arabic is between 60 and 70°C. At this temperature, gum becomes highly fluid and easy to stir. Excessive temperature leads to rapid moisture evaporation and higher energy consumption.

[0018] Preferably, in the preparation method of the copper sulfate paste, the heating temperature is 65°C. 65°C is a suitable minimum temperature.

[0019] Optionally, in the above preparation method, the thickener is gum arabic. Preferably, the mass ratio of gum arabic to water is 0.8~1.2.

[0020] Optionally, in the above preparation method, the humectant is glycerin. The glycerin raw material can be 100% glycerin or a certain concentration of aqueous glycerin solution, so that its final concentration in the copper sulfate ointment is 2-8%.

[0021] Fourthly, this application also provides the application of the aforementioned copper sulfate paste in the control of plant fungi. Its application method is quite flexible and can be used flexibly according to needs.

[0022] Alternatively, the application method is as follows: simply attach the side of the carrier coated with the paste or the cured paste sheet to the part of the plant to be treated and fix it in place.

[0023] Preferably, the copper sulfate paste is placed around the top of the plant branch to be treated, with the paste fixed at the very top. This arrangement ensures that the copper sulfate is slowly released and acts on almost all parts of the plant branch, maximizing the treatment area.

[0024] The present invention has the following beneficial effects: The copper sulfate ointment provided by this invention combines the chemical properties of copper sulfate with the physical advantages of an ointment formulation, and has the following significant advantages: 1. Highly effective sustained release, long-lasting effect Controlled release: The paste-like matrix can slow down the dissolution rate of copper sulfate, prolong the action time of the active ingredient, and reduce the frequency of copper sulfate application.

[0025] Long-lasting effect: Suitable for scenarios requiring continuous sterilization / bacteriostasis, such as apple branch rot and ring rot pathogen spores that are continuously infected by rainwater. Copper sulfate ointment avoids the reduction in efficacy caused by a sudden drop in agent concentration.

[0026] 2. Precise application to reduce waste Strong adhesion: The paste can adhere tightly to plant branches and twigs, reducing the loss of copper sulfate caused by external forces.

[0027] Local targeting: Apply directly to the affected area (such as apple rot lesions) to increase the local concentration of copper sulfate. When washed by rainwater, the copper sulfate dissolves into the rainwater and flows with the pathogen spores, which can kill the pathogen spores in the rainwater.

[0028] 3. Enhanced security Reduced ecotoxicity: The slow-release properties reduce the impact of the instantaneous release of copper ions on non-target biological communities (such as beneficial microorganisms in the soil, earthworms, etc.).

[0029] Operational safety: The paste-like form avoids the risk of inhaling copper sulfate dust as is common in conventional applications, making it safer.

[0030] 4. Environmental adaptability optimization Rain erosion resistant: Suitable for high humidity or outdoor environments, and more resistant to rain erosion than sprayed copper sulfate.

[0031] Temperature stability: The paste may offer better high / low temperature stability, avoiding crystallization or decomposition.

[0032] 5. Diverse application scenarios Suitable for special environments: Can be used on uneven surfaces (such as cracks in tree bark) and other scenarios where liquid agents are difficult to adhere to.

[0033] Mixed functionality: It is easy to combine with other ointment-like agents (such as bactericides + healing agents) to form multi-effect formulations.

[0034] 6. Economy and convenience Reduced dosage: Efficiently utilizes active ingredients, reducing the cost per unit area.

[0035] Convenient for storage and transportation: It typically saves more space than liquids and has no risk of leakage.

[0036] 7. Adjust the sustained-release rate as needed. The rate of copper ion release can be adjusted by coating a copper sulfate carrier to meet practical application requirements. For example, if gauze is used as the carrier, its strong water absorption capacity leads to rapid release of the active ingredient in copper sulfate; if non-woven fabric is used as the carrier, its weak water permeability results in slow release of the active ingredient. Attached Figure Description

[0037] Figure 1 The images show copper sulfate pastes prepared using guar gum (a), xanthan gum (b), and gum arabic (c) as thickeners, respectively. The three images from left to right in groups a, b, and c are, respectively, the copper sulfate paste, the paste before dissolution, and the copper sulfate paste after dissolution with water. Figure 2 The copper ion content of the leaching solution at different leaching times; Figure 3 The effects of different leaching solutions on the germination of anthracnose leaf blight pathogen spores; Figure 4 The effects of different leaching solutions on the germination of spores of the brown spot pathogen; Figure 5 The effects of different leaching solutions on the germination of spores of the pathogen causing ringworm; Figure 6 The effects of different leaching solutions on the germination of spores of the pathogen *Aureobasidium niger*; Figure 7 The efficacy of different leaching solutions in controlling apple anthracnose leaf blight; Figure 8 The results show the formation of a film on fruit trees by copper sulfate paste; where A represents the film formed by copper sulfate paste on apple tree branches and trunks, and B represents the control effect of copper sulfate paste on apple tree branch canker. Detailed Implementation

[0038] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. In the present invention, unless otherwise specified, the equipment and raw materials used can be purchased from the market or are commonly used in the art. Unless otherwise specified, the methods in the following embodiments are conventional methods in the art.

[0039] Example 1: Preparation of Copper Sulfate Ointment 1. This embodiment uses a copper sulfate ointment, which includes the following components: 100g of gum arabic, 10g of copper sulfate, 10mL of glycerin (i.e., 12.6g of glycerin) and 100ml (i.e., 100g) of deionized water.

[0040] In this embodiment, the copper sulfate ointment comprises the following components by mass fraction: 50 parts gum arabic (44.9%), 5 parts copper sulfate (4.4%), 6.3 parts glycerin (5.6%), and 50 parts water (44.9%). (The percentages in parentheses are the mass percentages of each component.) 2. The preparation method of the copper sulfate paste includes the following steps: S1. Place 100g of gum arabic into a 500ml beaker, pour in 100ml of deionized water, and soak at room temperature for 8-12 hours to allow the gum arabic to fully absorb water and swell. Then place the beaker in a 65℃ water bath and heat while stirring to completely dissolve the gum arabic and form a uniform and transparent solution. S2. Slowly add 10g of copper sulfate powder to the adhesive solution prepared in the previous step, while heating and stirring, keeping the temperature at around 65℃, until the copper sulfate powder is evenly dispersed in the adhesive solution and the adhesive solution turns brown. S3. Add 10 mL of glycerin to the beaker and continue stirring until homogeneous to prepare copper sulfate paste. S4. Pour the copper sulfate paste with adjusted viscosity into a mold to form the preset shape; alternatively, the copper sulfate paste can be directly and evenly applied to a carrier material to prepare a copper sulfate plaster.

[0041] The carrier material can be selected from absorbent and breathable materials such as gauze or non-woven fabric.

[0042] Example 2: Optimization of Copper Sulfate Ointment and its Preparation Method Copper sulfate ointment mainly consists of copper sulfate, thickeners, water, and humectants. To successfully prepare a copper sulfate ointment with good sustained-release effect, long-lasting effect, and simple and easy-to-use formulation, the effects of different components on the copper sulfate ointment were studied, and the following formulation experiments were conducted: 1. Screening of thickeners (1) Experimental methods This experiment selected three commonly used thickeners: guar gum, xanthan gum, and gum arabic. Copper sulfate pastes were prepared according to the following methods (named Groups 1-3 respectively), and the sustained-release properties of the copper sulfate pastes were tested by leaching.

[0043] Group 1: Pour 50ml of water into a 100ml beaker, add 1g of guar gum, and stir with a glass rod until a transparent colloid is formed. Weigh 0.5g of copper sulfate powder, add a small amount of water, and heat while stirring until the copper sulfate dissolves. Pour the dissolved copper sulfate into the guar gum and stir until a green colloid is formed. Add 500μL of glycerin as a moisturizer. Apply the paste evenly to a double layer of gauze with a brush and attach it to the trunk of the apple tree.

[0044] Group 2: Pour 50ml of water into a 100ml beaker, add 2g of xanthan gum, and stir with a glass rod until a transparent colloid is formed (a small amount of xanthan gum will not dissolve; let it swell fully for a period of time). Weigh 0.5g of copper sulfate powder, add a small amount of water, and heat while stirring until the copper sulfate dissolves. Pour the dissolved copper sulfate into the xanthan gum and stir until a blue colloid is formed. Add 500μL of glycerin, stir well, and then use a brush to evenly spread the paste on a double layer of gauze and attach it to the trunk of the apple tree.

[0045] Group 3: Place 15g of gum arabic in a 50ml beaker, pour in 15ml of deionized water, and soak overnight at room temperature to allow the gum arabic to fully absorb water and swell. Then heat and stir in a 65℃ water bath until the gum arabic is completely dissolved, forming a uniform and transparent solution. Add 0.3g of copper sulfate powder to the dissolved gum arabic, heating and stirring continuously until the copper sulfate is evenly dispersed in the solution, which turns brown. Add 300μL of glycerin and continue stirring until the plaster has better flexibility. Spread the prepared copper sulfate ointment onto double-layered gauze to make a copper sulfate plaster.

[0046] (2) Experimental results and analysis Group 1: Copper sulfate paste made with guar gum as a thickener. After being dissolved by water spraying, the paste flowed out in large quantities in a short time, with poor slow-release effect and the colloid could not be evenly adhered to the tree surface.

[0047] Group 2: Copper sulfate paste made with xanthan gum as a thickener cannot absorb water and flow out after being sprayed with water, thus preventing the release of copper sulfate.

[0048] Furthermore, because guar gum and xanthan gum have strong water absorption capabilities, the amount of thickener in the resulting pastes is low. Under natural conditions, after losing water due to wind and sun exposure, copper sulfate pastes made from these two ingredients require a large amount of water absorption to release copper sulfate, which does not meet the requirements for the function of sulfuric acid pastes.

[0049] Copper sulfate ointment made with gum arabic as a thickener slowly flows out after being dissolved by water spraying, thus achieving a slow-release effect of copper sulfate. Furthermore, gum arabic has low water absorption capacity; as a thickener, its content in the copper sulfate ointment is 40%, and it dissolves and flows out easily in water under natural conditions, meeting the sterilization target of copper sulfate ointment. Therefore, gum arabic was selected as the thickener for copper sulfate ointment.

[0050] 2. Screening for gum arabic content (1) Experimental methods To prepare gum arabic with the appropriate viscosity, it is necessary to first dissolve the gum arabic in water. Experiments were conducted to screen the amount of water to be added, and three ratios of gum arabic to water were set: 1:2, 1:1, and 2:1.

[0051] (2) Experimental results and analysis The results showed that when gum arabic was mixed with water in a 1:2 ratio and heated and stirred in a 65°C water bath, the resulting colloid was too thin to form a solid paste and could not adhere to the tree trunk. When the ratio of gum arabic to water was 2:1, the resulting colloid was too viscous to dissolve copper sulfate, making it difficult to apply to surfaces such as gauze to form a plaster. When the ratio of gum arabic to water was 1:1, the resulting colloid had a suitable viscosity, dissolved copper sulfate, and could adhere to gauze to form a plaster.

[0052] Therefore, the final determination of the mass ratio of gum arabic to water in copper sulfate paste was 0.8~1.2.

[0053] 3. Method of adding copper sulfate (1) Experimental methods In the preparation of copper sulfate paste, try the following two methods to add copper sulfate to gum arabic solution (gum arabic:water = 6:4): A added 5% copper sulfate by weight of the adhesive directly to the dissolved gum arabic and stirred. The copper sulfate could not be completely dissolved, and the residual crystals caused the paste to have a noticeable grainy texture. The copper sulfate was not evenly distributed in the colloid.

[0054] Alternatively, in step B, heat the same amount of gum arabic solution in a water bath. Once the solution temperature reaches 65°C, immediately and slowly add the same amount of copper sulfate as in step A while continuously stirring. The copper sulfate will dissolve completely, forming a brown solution.

[0055] (2) Experimental results and analysis The experimental results indicate that the optimal method for adding copper sulfate is to slowly add it to the gum arabic solution while continuously stirring in a water bath at 65°C until the copper sulfate is completely dissolved.

[0056] 4. Screening of stretching agents (1) Experimental methods Three treatment groups were set up: one with no glycerin, one with 5% glycerin by weight, and one with 10% glycerin by weight. Copper sulfate ointment was prepared in the three treatment groups according to the method described in Example 1 above.

[0057] (2) Experimental results and analysis ① In the treatment group without glycerin, the copper sulfate paste shrank and cracked after drying, resulting in reduced adhesion to tree branches and trunks, and it was easy to fall off in chunks.

[0058] ② In the treatment group with 5% glycerin added to the total mass, the copper sulfate paste has good extensibility, strong adhesion to tree branches and trunks, and does not crack.

[0059] ③ In the treatment group with 10% glycerin added by total mass, the viscosity of copper sulfate paste decreased, its formability was reduced, and it was easy to melt and run off when it was applied to tree branches and trunks after being exposed to the sun.

[0060] Therefore, the amount of glycerin added is determined to be 2-8% of the total amount of the ointment. The addition of glycerin ensures that the viscosity of the copper sulfate ointment meets the requirements of being spreadable, not dripping, and resistant to erosion.

[0061] Based on the above-mentioned multiple sets of optimization experiments, the formulation and preparation method of the copper sulfate ointment in Example 1 were finally obtained.

[0062] Example 3: Test of the sustained-release ability of copper sulfate ointment 1. Experimental Methods In the experimental group, the prepared copper sulfate paste from Example 1 was pressed onto apple branches approximately 2 cm in diameter. The branches were fixed to a test tube rack, and a beaker was used to collect the solution dripping from the branches. Deionized water was slowly rinsed down the paste-coated area multiple times, with each rinse consisting of 20 ml of water. A control group was prepared using copper sulfate powder wrapped in double layers of gauze. The gauze was wrapped around the tree trunk, and the rinsing method was the same as for the paste.

[0063] The copper ion content was determined by selecting the first, eighth, and nineteenth leaching solutions from both the experimental and control groups.

[0064] The copper sulfate content in the leached solution was determined using the EDTA method. Specifically, 1 ml of the leaching solution was taken, and PAN indicator was added until the solution turned purple-red. The solution was then titrated with EDTA standard solution until it changed from purple-red to bright yellow. The amount of copper ions was calculated based on the amount of EDTA used in the titration.

[0065] 2. Experimental Results and Analysis The experimental results are shown in Figure 2 The results showed that the control group contained a large amount of copper ions in the first leaching, with a copper ion concentration of 0.06 mol / L. Copper ions were undetectable in the eighth leaching solution, indicating that the copper sulfate powder was completely dissolved, and the pure copper sulfate powder dissolved rapidly with the water flow. In contrast, the copper ion concentration in the first and eighth leaching solutions of the copper sulfate paste was basically the same, both at 0.004 mol / L. A small amount of copper ions was still detectable in the nineteenth leaching solution, with a concentration of 0.0005 mol / L. These results indicate that the copper sulfate paste provided in this application has a stable copper sulfate content and is released continuously and slowly. This copper sulfate paste has a good sustained-release effect and is rain-resistant.

[0066] Example 4: Experiment on the inhibition of fungal spore germination by copper sulfate ointment solution Most plant fungal diseases spread through the germination and infection of pathogenic spores. This experiment was designed to verify the inhibitory effect of copper sulfate ointment leaching solution on fungal spore germination.

[0067] 1. Experimental subjects: Anthracnose leaf blight pathogen spores, apple brown spot pathogen spores, apple ring rot pathogen spores, and apple black spot pathogen spores were selected as experimental materials.

[0068] 2. Experimental Methods This experiment tested the effects of different leaching solutions obtained in Example 3 on the germination of spores of *Anthracnose leaf blight* pathogen of apples. The same mass of copper sulfate powder wrapped in double-layered gauze served as a control group. The specific method was as follows: (1) Effect of copper sulfate ointment leaching solution on spore germination of anthracnose leaf blight pathogen. Conidia were induced in various pathogens on Richard medium. Anthracnose leaf blight colonies were crushed into small pieces using sterile toothpicks and placed in Richard medium. The mixture was incubated for 3 days at 25°C and 180 rpm on a shaker, resulting in abundant conidia production. The conidia were filtered through four layers of sterile gauze into 50 ml centrifuge tubes and centrifuged at 5000 rpm for 5 min. The resulting orange-yellow conidia precipitate was used to prepare a spore suspension. The concentration of the spore suspension was adjusted to 1 × 10⁻⁶ with purified water. 5Spores / mL. The leaching solutions from the 1st, 8th, and 19th leachings in Example 3 were mixed 1:1 with the conidial suspension, with a conidial suspension containing added pure water serving as a control. 50 µL of the treated spore suspension was dropped onto a glass slide, with 3 slides for each treatment. One drop of spore suspension was placed on each end of each slide, and the slides were placed in a humidification box to maintain 100% relative humidity. The spore germination rate was observed after 24 hours.

[0069] (2) Effect of copper sulfate ointment leaching solution on spore germination of apple brown spot pathogen. Fresh brown spot diseased leaves, which had been cultured at 25℃ with humidity and showed a large amount of spores, were soaked in purified water to prepare a spore suspension. The concentration of the spore suspension was adjusted to 1×10⁻⁶. 5 spores / mL. The spore suspension was mixed with copper sulfate leaching solution at a 1:1 ratio, and the spore suspension was mixed with purified water at a 1:1 ratio as a control. The mixture was dropped onto a glass slide, three slides for each treatment, and placed in a humidification box. After 24 hours in an incubator at 25°C, the spore germination rate was measured.

[0070] (3) Effect of copper sulfate ointment leaching solution on the germination of *Chaetoceros maculata* spores Effect of copper sulfate ointment on the germination of *Rhizoctonia solani* spores: *Rhizoctonia solani* spores were collected from apples that had produced spores after induction under black light. A spore suspension was prepared using purified water, and the concentration of the spore suspension was adjusted to 1×10⁻⁶. 5 spores / mL. A 1:1 mixture of spore suspension and copper sulfate leaching solution was used, and a 1:1 mixture of spore suspension and water was used as a control. Three slides were dropped onto glass slides for each treatment, placed in a humidity chamber, and incubated at 25°C for 24 hours. Spore germination rate was then measured. (4) Effect of copper sulfate ointment leaching solution on the germination of black spot fungus spores Spores were collected from fresh leaves infected with black spot disease. A spore suspension was prepared using purified water, and the concentration of the spore suspension was adjusted to 1×10⁻⁶. 5 spores / mL. The spore suspension was mixed with copper sulfate leaching solution at a 1:1 ratio, and the spore suspension was mixed with purified water at a 1:1 ratio as a control. The mixture was dropped onto a glass slide, three slides for each treatment, and placed in a humidification box. After 24 hours in an incubator at 25°C, the spore germination rate was measured.

[0071] 3. Experimental Results The results are as follows: Figures 3-6 As shown, compared with the high germination rate of the control group, the spore germination rate of copper sulfate ointment remained below 2.0% from the first to the 19th leaching. This indicates that copper sulfate ointment leaching has a significant inhibitory effect on the germination of various fungal spores, and is slow-released with a long-lasting effect.

[0072] In the control group, the first leaching of copper sulfate powder significantly inhibited spore germination, but the inhibitory effect decreased significantly by the eighth leaching, and the spore germination rate increased significantly. This indicates that the control group did not have a copper sulfate slow-release effect, and the copper sulfate was lost too quickly and excessively.

[0073] The results above show that the copper sulfate ointment provided in this application slowly releases copper sulfate with the water flow, maintaining its inhibitory effect on pathogen spore germination. It also indicates that there is no difference in the inhibitory effect on spore germination between low-concentration copper sulfate in the ointment solution and high-concentration copper sulfate in the powder solution; the ointment is more effective in utilizing and slowly releasing the active ingredient of copper sulfate, thus prolonging the duration of its inhibitory effect on pathogen spore germination.

[0074] Example 5. The control effect of copper sulfate ointment on fungal diseases. This experiment was conducted to verify whether copper sulfate ointment leaching solution has a control effect on plant pathogenic fungi. Since copper sulfate has a broad-spectrum inhibitory effect on fungal diseases, this example uses apple anthracnose leaf blight as the model pathogen to test the control effect of the copper sulfate ointment.

[0075] 1. Experimental Methods The induction of conidia and preparation of the conidia suspension of *Anthracnose leaf blight* were carried out in the same manner as in Example 4, yielding a concentration of 1×10⁻⁶. 5 A conidial suspension of 1 / mL was used for inoculation experiments. Healthy 'Gala' apple leaves of similar age were selected, surface-sterilized with 75% alcohol, and air-dried. The leaves were then immersed in the spore suspension for 30 seconds, removed, and air-dried again. The spore suspension consisted of the 1st, 8th, and 19th spore suspensions from Example 3. The conidial suspension was sprayed evenly onto the leaf surface using a spray bottle until droplets fell. The leaves were incubated at a constant temperature and humidity of 25°C. After 3 days, the disease incidence on the leaves was observed and recorded. Three leaves were used for each treatment, and the experiment was repeated three times.

[0076] Leaves soaked in water served as a blank control, while copper sulfate powder leaching solution served as a degradation control.

[0077] 2. Experimental Results and Analysis The results are as follows Figure 7 As shown, in the control group, the leaves were clearly infected by the pathogen of apple anthracnose leaf blight, and covered with lesions. In the copper sulfate powder experimental group, although the first drenching solution was effective in controlling anthracnose leaf blight, the eighth drenching solution was ineffective in controlling the disease because it was washed away too quickly and had no slow-release effect. However, the first, eighth, and nineteenth drenching solutions of copper sulfate paste showed significant control effects on anthracnose leaf blight.

[0078] Therefore, compared with copper sulfate powder, the copper sulfate paste of this application can continuously and slowly release copper ions, avoiding the large-scale release of copper ions with water flow, reducing the amount of copper sulfate used and the risk of soil pollution.

[0079] Example 6: Field application effects of copper sulfate paste and its control effect on apple branch and trunk diseases. 1. Experimental Methods The prepared copper sulfate paste is evenly spread on the surface of double-layered gauze, with a paste thickness of about 2mm, to make a copper sulfate plaster. The prepared plaster is then applied to apple trees with branch ring rot caused by Botrytis cinerea, allowing it to be washed away by rainwater.

[0080] 2. Experimental Results and Analysis Figure 8 The results showed that the copper sulfate paste could withstand rain erosion for two months. The mixture of gum arabic and copper sulfate, washed away by rain, remained uniformly on the trunk due to its adhesiveness, forming a film. Because the paste partially dissolved into liquid upon contact with rain, it penetrated into bark crevices and cracks caused by lesions, resulting in a wide application area. The film on the trunk surface remained resistant to rain erosion and maintained its effectiveness for two months. The film contained copper sulfate, which had a significant preventative effect against trunk and branch diseases.

[0081] from Figure 8 The results showed that on the branches below the point where the plaster was applied (forming a protective film), the ring rot lesions did not expand and slowly healed; however, on the branches above the plaster, the lesions continued to expand, and the branch bark became necrotic. Compared with the branches protected by the protective film, the ring rot was significantly more severe. This result indicates that copper sulfate plaster, when prepared as a paste, can slowly release copper sulfate in the field, and has a significant effect on the control of branch ring rot.

[0082] It is understood that those skilled in the art can make equivalent substitutions or modifications to the technical solutions and concepts of this invention, and all such substitutions or modifications should fall within the protection scope of the appended claims.

Claims

1. A copper sulfate paste, characterized in that, It includes the following components in parts by weight: 1-10 parts copper sulfate, 40-50 parts thickener, and 2-8 parts humectant, with water as the solvent.

2. The copper sulfate paste according to claim 1, characterized in that, The thickener is gum arabic.

3. The copper sulfate paste according to claim 2, characterized in that, In the copper sulfate paste, the mass ratio of gum arabic to water is 0.8~1.

2.

4. The copper sulfate paste according to claim 1, characterized in that, The moisturizer is glycerin with a mass percentage concentration of glycerin.

5. A copper sulfate ointment patch, characterized in that, It includes a carrier material and a copper sulfate paste as described in claims 1 to 4, which is uniformly coated on the surface of the carrier.

6. The copper sulfate ointment patch according to claim 1, characterized in that, The carrier material is a flexible material that can adsorb or adhere to copper sulfate paste.

7. The method for preparing copper sulfate paste according to claims 1-4, characterized in that, Includes the following steps: S1. Place the corresponding amount of thickener into the corresponding amount of distilled water and soak at room temperature for 8-12 hours to allow the thickener to fully absorb water and swell; then heat and stir to completely dissolve the thickener and form a uniform and transparent gel; the heating temperature is 60-70℃. S2. Slowly add copper sulfate powder to the adhesive solution prepared in the previous step, while heating and stirring, until the copper sulfate powder is evenly dispersed in the adhesive solution; the heating temperature is 60~70℃. S3. Add a humectant to the adhesive solution to make the final mass percentage concentration of the humectant 2%~8%, and continue to stir evenly to prepare copper sulfate paste. S4. Forming of copper sulfate paste: Pour the copper sulfate paste with adjusted viscosity into a mold to form a shape that is easy to use; alternatively, the copper sulfate paste can be directly applied to a carrier material to prepare a copper sulfate plaster.

8. The method for preparing copper sulfate paste according to claim 7, characterized in that, The heating temperature is 65℃.

9. The application of the copper sulfate ointment as described in claim 1 in the control of plant fungi.

10. The application according to claim 9, characterized in that, The application method is as follows: apply the side of the carrier coated with the paste or the cured paste sheet to the part of the plant to be treated.

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