Anti-cracking coating for cover sheet with liquid storage tank and anti-cracking cover sheet

Abstract

The present invention relates to the field of biological experimental equipment and discloses an anti-cracking coating for a cover sheet with a liquid reservoir and an anti-cracking cover sheet. The anti-cracking coating comprises component A and component B; component A comprises an epoxy resin; component B comprises modified silica, wherein the modified silica is silica having a fluorocarbon-based hydrophobic and oleophobic layer and a polyamino polymer grafted onto its surface; before the anti-cracking coating is applied to the inner wall of the liquid reservoir of the cover sheet, the inner wall of the liquid reservoir is pretreated to form carboxyl groups on the inner wall surface of the liquid reservoir. Using the coating of the present invention to form a coating on the inner wall of the liquid reservoir of the cover sheet can effectively reduce cracking or deformation of the cover sheet and improve the durability of the cover sheet.

Description

Technical Field

[0001] The invention relates to the field of biological experimental equipment, in particular to an anti-cracking coating for a cover sheet with a liquid storage tank and the anti-cracking cover sheet. Background Art

[0002] The cover slip is one of the commonly used instruments in biological experiments. After placing the sample on the slide and covering it with the cover slip, it can be placed under a microscope for observation, which can avoid the sample from contaminating the microscope and facilitate the observation of the sample. A cover slip with a liquid reservoir (such as the biological cover slip provided in patent CN201721357888.X) can provide a place for the reaction and can be used for immunohistochemical reactions, in situ hybridization reactions, and special staining reactions. When in use, the cover slip is attached to the surface of the slide, and a chamber is formed between the liquid reservoir in the cover slip and the slide. The reaction solution is injected into the chamber through the liquid filling port, and the reaction can be carried out in the chamber.

[0003] During use, the reservoir comes into contact with organic liquids (such as the drag solution used in immunohistochemistry experiments), causing the dissolution of small molecules such as plasticizers, which in turn causes the cover slip to crack or deform. According to experiments conducted by the present invention team, most cover slips currently crack or deform after being used less than 15 times in immunohistochemistry experiments. A few high-quality cover slips can reach about 25 times, which still cannot meet the needs of long-term use. Therefore, it is of great significance to provide a method for preventing cover slips from cracking. Summary of the Invention

[0004] To address the technical problem of existing cover sheets having a limited number of uses and being prone to cracking or deformation after repeated use, the present invention provides an anti-cracking coating for a cover sheet with a liquid reservoir. This coating forms a coating on the inner wall of the cover sheet's liquid reservoir, effectively slowing cracking or deformation of the cover sheet and improving its durability.

[0005] The specific technical solutions of the present invention are:

[0006] In a first aspect, the present invention provides an anti-cracking coating for a cover sheet with a liquid reservoir, comprising component A and component B; component A comprises an epoxy resin; component B comprises modified silica, wherein the modified silica is silica having a fluorocarbon-based hydrophobic and oleophobic layer and a polyamino polymer grafted on its surface; before the anti-cracking coating is applied to the inner wall of the liquid reservoir of the cover sheet, the inner wall of the liquid reservoir is pretreated to form carboxyl groups on the surface of the inner wall of the liquid reservoir.

[0007] When the coating of the present invention is used to form a coating on the inner wall of the cover sheet liquid reservoir, a rough surface can be constructed using silicon dioxide, and a fluorocarbon-based hydrophobic and oleophobic layer grafted on the silicon dioxide can be used to give the coating hydrophobic and oleophobic properties. While exerting a physical barrier effect, this coating can also utilize its hydrophobic and oleophobic properties to reduce the penetration of organic solutions, thereby reducing the contact between the organic solution and the cover sheet. In addition, the hydrophobic and oleophobic properties of the coating can also repel small molecules such as plasticizers. Under the above combined effects, the dissolution of small molecules such as plasticizers in the cover sheet can be slowed down, thereby improving the durability of the cover sheet and slowing down the cracking or deformation of the cover sheet.

[0008] The bonding strength of the coating on the surface of the cover sheet is limited, the silica particles grafted with a fluorocarbon-based hydrophobic and oleophobic layer are easy to fall off, and the coating is easily destroyed, resulting in a decrease in the hydrophobic and oleophobic properties of the coating and the physical barrier effect, thereby affecting the durability of the cover sheet. In this regard, the present invention grafts a polyamino polymer on the surface of the silica, and forms a carboxyl group on the inner wall surface of the cover sheet reservoir by pretreatment before the coating is used, which can play the following roles: during the curing of the coating, the amino group in the polyamino polymer can react with the epoxy group in the epoxy resin to form a covalent bond between the modified silica and the epoxy resin; and, when the coating is applied, the amino group in the polyamino polymer can be bound to the carboxyl group on the inner wall surface of the reservoir by electrostatic attraction and hydrogen bonding. In this way, the bonding strength of the epoxy resin and the modified silica on the surface of the cover sheet can be improved, making the modified silica less likely to fall off and the coating less likely to be damaged, thereby improving the durability of the cover sheet to a greater extent.

[0009] In addition, the present invention grafts a polyamino polymer onto silica instead of dispersively grafting small molecules with a small amount of amino groups onto silica. This ensures the bonding strength of the modified silica on the cover sheet while making the distribution of amino groups on the silica surface relatively concentrated, thereby reducing the masking and damage of the fluorocarbon-based hydrophobic and oleophobic layer, and improving the effect of the coating in slowing down the dissolution of small molecules such as plasticizers in the cover sheet.

[0010] Preferably, the component A comprises the following ingredients in parts by weight: 80-100 parts of epoxy resin and 23-35 parts of solvent A; the component B comprises the following ingredients in parts by weight: 16-25 parts of modified silica, 3-5 parts of amine curing agent, 0-5 parts of compound containing amino and perfluoro groups, and 20-30 parts of solvent B; the mass ratio of the component A to the component B is 4-6:1.

[0011] Compounds containing amino groups and perfluorinated groups can utilize the amino groups therein to be grafted onto epoxy resins to improve the hydrophobicity and oleophobicity of the coating.

[0012] Preferably, the compound containing an amino group and a perfluorinated group is one or more of perfluorooctane, 1H,1H-perfluorononylamine and 1H,1H,2H,2H-perfluorodecylamine.

[0013] Preferably, the silicon dioxide comprises silicon dioxide having a mass ratio of 1:1 to 1.5 and a particle size D90 of 5 to 15 nm and 90 to 120 nm, respectively.

[0014] Preferably, the preparation method of the modified silicon dioxide comprises the following steps:

[0015] (1) using triethylenetetramine and methyl acrylate as monomers, performing a polymerization reaction to prepare a polyamino polymer;

[0016] (II) grafting a silane coupling agent onto the surface of silica, wherein the silane coupling agent includes a fluorocarbon-based silane coupling agent and an acrylate-based silane coupling agent to prepare a fluorocarbon-based / acrylate-based composite modified silica;

[0017] (III) utilizing the addition reaction between amino groups and acrylate groups to graft the polyamino polymer onto the fluorocarbon-based / acrylate-based composite modified silica to prepare the modified silica.

[0018] The mechanism of the above preparation process is as follows: in step (I), the amino group and secondary amino group in triethylenetetramine can undergo addition reaction with the carbon-carbon double bond in methyl acrylate, and the amino group in triethylenetetramine can undergo amine-ester exchange reaction with the -COOCH3 group in methyl acrylate, thereby preparing a polyamino polymer; in step (II), the silanol group on the surface of silica can react with the silanol group formed after hydrolysis of the silane coupling agent, thereby grafting the fluorocarbon group and the acrylate group onto the silica, wherein the fluorocarbon group can form a hydrophobic and oleophobic layer on the surface of the silica; in step (III), the amino group in the polyamino polymer can undergo addition reaction with the carbon-carbon double bond in the acrylate group, thereby grafting a polyamino molecular chain onto the silica.

[0019] Preferably, step (I) specifically includes the following steps: mixing triethylenetetramine and solvent I, cooling to 0-7°C, adding methyl acrylate dropwise thereto, and then reacting at 20-30°C for 4-5 hours; removing solvent I, and reacting at 70-80°C for 40-50 minutes to obtain a polyamino polymer.

[0020] During the polycondensation reaction at 70-80°C, if the reaction time is too long, the polyamino polymer molecules are large, which can easily damage the hydrophobic and oleophobic layer on the surface of the modified silica, causing the hydrophobic and oleophobic properties of the coating to decrease, thereby affecting the durability of the cover sheet. If the reaction time is too short, the number of amino groups in the polyamino polymer molecules is small, and the bonding strength of the modified silica to the cover sheet decreases, which also affects the durability of the cover sheet. Based on this, the present invention controls the time of the polycondensation reaction so that the modified silica can improve the durability of the cover sheet to a greater extent.

[0021] Furthermore, in step (I), the molar ratio of methyl acrylate to triethylenetetramine is 1:1.5-2.5.

[0022] Preferably, step (II) specifically includes the following steps: dispersing silica in solvent II, adjusting the pH to 7.5-8.5, adding a silane coupling agent, reacting at 50-60° C. for 4-6 hours, separating the product, and obtaining a fluorocarbon-based / acrylate-based composite modified silica.

[0023] Preferably, in step (II), the silane coupling agent comprises a fluorocarbon-based silane coupling agent, an acrylate silane coupling agent, and an alkyl silane coupling agent in a molar ratio of 1:0.03-0.05:0-0.3; and the mass ratio of the silica to the silane coupling agent is 1:3-5.

[0024] Preferably, in step (II), the fluorocarbon-based silane coupling agent is 1H,1H,2H,2H-perfluorodecyltriethoxysilane; the acrylate silane coupling agent is one or more of 3-(methacryloyloxy)propyltrimethoxysilane, 3-(acryloyloxy)propyltrimethoxysilane and 3-(methacryloyloxy)propyltriethoxysilane; and in the alkyl silane coupling agent, the number of carbon atoms in the alkyl chain is 8 to 10.

[0025] Preferably, step (III) specifically comprises the following steps: dispersing the fluorocarbon-based / acrylate-based composite modified silica into solvent III, adding a polyamino polymer, and reacting at 30-50° C. for 1.5-2.5 hours to obtain modified silica.

[0026] Furthermore, in step (III), the mass volume ratio of the fluorine-containing group / acrylate-based composite modified silica, the polyamino polymer, and the solvent III is 1 g: 0.06-0.10 g: 15-20 mL.

[0027] Preferably, the cover sheet is made of polycarbonate; and the pretreatment method is to irradiate with ultraviolet light having a wavelength of 200 to 275 nm.

[0028] Polycarbonate is a commonly used material for cover sheets. UV light irradiation can form carboxyl and hydroxyl groups on the surface of the polycarbonate cover sheet. The carboxyl groups can bind to the amino groups on the surface of the modified silica prepared in this invention through electrostatic attraction and hydrogen bonding. The hydroxyl groups can also form hydrogen bonds with the amino groups on its surface, thereby increasing the bonding strength of the modified silica to the cover sheet.

[0029] Furthermore, the ultraviolet light irradiation time is 15 to 30 minutes.

[0030] In a second aspect, the present invention provides a use of the anti-cracking coating in an anti-cracking cover sheet with a liquid storage tank.

[0031] Preferably, the application comprises the following steps:

[0032] S1: pre-treating the inner wall of the liquid reservoir in the cover sheet to form carboxyl groups on the inner wall surface of the liquid reservoir;

[0033] S2: Component A and component B are mixed, applied to the inner wall of the liquid reservoir in the cover sheet, and then cured at 30-40° C. for 1.5-2.5 hours, and dried to obtain an anti-cracking cover sheet.

[0034] Compared with the prior art, the present invention has the following advantages:

[0035] (1) After the coating of the present invention forms a coating on the inner wall of the cover sheet liquid reservoir, it can slow down the dissolution of small molecules such as plasticizers in the cover sheet through physical barrier effect and hydrophobicity and oleophobicity, thereby improving the durability of the cover sheet;

[0036] (2) The present invention adopts a multi-amino polymer grafting modification method, which can improve the bonding strength of the modified silica on the cover sheet, and at the same time reduce the masking and damage of the amino grafting to the fluorocarbon-based hydrophobic and oleophobic layer on the silica surface, so that the coating can greatly improve the durability of the cover sheet. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a photograph of the coverslip after 50 immunohistochemical experiments in Examples 1 to 3;

[0038] Figure 2 This is a photograph of the coverslip after 43 rounds of immunohistochemistry experiment in Example 4;

[0039] Figure 3 This is a photograph of the coverslip after 40 immunohistochemistry experiments in Example 5;

[0040] Figure 4 This is a photograph of the coverslip after 16 immunohistochemistry experiments in Comparative Example 1;

[0041] Figure 5 This is a photograph of the coverslip after 39 immunohistochemistry experiments in Comparative Example 2;

[0042] Figure 6 This is a photograph of the coverslip after 24 immunohistochemistry experiments in Comparative Example 3. DETAILED DESCRIPTION

[0043] The present invention will be further described below with reference to the embodiments.

[0044] Overall embodiment

[0045] An anti-cracking coating for a cover sheet with a liquid storage tank comprises component A and component B; component A comprises epoxy resin; component B comprises modified silicon dioxide, wherein the modified silicon dioxide is silicon dioxide with a fluorocarbon-based hydrophobic and oleophobic layer and a polyamino polymer grafted on the surface.

[0046] As a specific embodiment, the component A includes the following ingredients in parts by weight: 80-100 parts of epoxy resin and 23-35 parts of solvent A; the component B includes the following ingredients in parts by weight: 16-25 parts of modified silica, 3-5 parts of amine curing agent, 0-5 parts of a compound containing an amino group and a perfluoro group (one or more of perfluorooctane, 1H,1H-perfluorononylamine and 1H,1H,2H,2H-perfluorodecylamine can be selected), and 20-30 parts of solvent B; the mass ratio of the component A to the component B is 4-6:1.

[0047] As a specific embodiment, the silicon dioxide includes silicon dioxide having a mass ratio of 1:1 to 1.5 and a particle size D90 of 5 to 15 nm and 90 to 120 nm, respectively.

[0048] As a specific embodiment, the preparation method of the modified silicon dioxide comprises the following steps:

[0049] (1) using triethylenetetramine and methyl acrylate as monomers, performing a polymerization reaction to prepare a polyamino polymer;

[0050] (II) grafting a silane coupling agent onto the surface of silica, wherein the silane coupling agent includes a fluorocarbon-based silane coupling agent and an acrylate-based silane coupling agent to prepare a fluorocarbon-based / acrylate-based composite modified silica;

[0051] (III) utilizing the addition reaction between amino groups and acrylate groups to graft the polyamino polymer onto the fluorocarbon-based / acrylate-based composite modified silica to prepare the modified silica.

[0052] As a specific embodiment, step (I) specifically includes the following steps: mixing triethylenetetramine and solvent I, cooling to 0-7°C, adding methyl acrylate dropwise thereto, wherein the molar ratio of methyl acrylate to triethylenetetramine is 1:1.5-2.5, and then reacting at 20-30°C for 4-5 hours; removing solvent I, and reacting at 70-80°C for 40-50 minutes to obtain a polyamino polymer.

[0053] As a specific embodiment, step (II) specifically includes the following steps: dispersing silica in solvent II, adjusting the pH to 7.5-8.5, and then adding a silane coupling agent, wherein the silane coupling agent includes a fluorocarbon-based silane coupling agent (1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane can be selected), an acrylate silane coupling agent (one or more of 3-(methacryloyloxy)propyltrimethoxysilane, 3-(acryloyloxy)propyltrimethoxysilane and 3-(methacryloyloxy)propyltriethoxysilane can be selected) and an alkyl silane coupling agent (an alkyl silane coupling agent having 8 to 10 carbon atoms in the alkyl chain can be selected) in a molar ratio of 1:0.03-0.05:0-0.3, the mass ratio of the silica to the silane coupling agent is 1:3-5, the reaction is carried out at 50-60°C for 4-6 hours, and the product is separated to obtain a fluorocarbon-based / acrylate-based composite modified silica.

[0054] As a specific embodiment, step (III) specifically includes the following steps: dispersing the fluorocarbon-based / acrylate-based composite modified silica into solvent III, adding a polyamino polymer, wherein the mass volume ratio of the fluorocarbon-based / acrylate-based composite modified silica, the polyamino polymer, and the solvent III is 1g:0.06~0.10g:15~20mL, and reacting at 30~50°C for 1.5~2.5h to obtain modified silica.

[0055] Applying the above-mentioned anti-cracking coating to an anti-cracking cover sheet with a liquid reservoir comprises the following steps:

[0056] S1: pre-treating the inner wall of the liquid reservoir in the cover sheet to form carboxyl groups on the inner wall surface of the liquid reservoir;

[0057] S2: Component A and component B are mixed, applied to the inner wall of the liquid reservoir in the cover sheet, and then cured at 30-40° C. for 1.5-2.5 hours, and dried to obtain an anti-cracking cover sheet.

[0058] As a specific embodiment, the cover sheet is made of polycarbonate; in step S1, the pretreatment method is to irradiate with ultraviolet light with a wavelength of 200 to 275 nm for 15 to 30 minutes.

[0059] Example 1

[0060] The cover sheet with a liquid reservoir (the cover sheet structure is the same as Example 2 in the applicant's patent CN201721357888.X, the size of the liquid filling port is smaller than that shown in the drawings of the patent. After the cover sheet is attached to the specimen slide, the liquid reservoir and the specimen slide form the liquid storage cavity in the patent; the cover sheet is made of polycarbonate) is treated to prevent cracking. The steps are as follows:

[0061] S1: Preparation of modified silica:

[0062] S1.1: Take triethylenetetramine and methanol in a mass-to-volume ratio of 1g:1mL, mix them and place them in an ice bath. After cooling to 7℃, control the temperature at 2.5±1.5℃, take methyl acrylate with a mass of 1 / 3 of triethylenetetramine and add it dropwise. After the addition is complete, control the temperature at 22±0.5℃ and stir for 5h; then remove the methanol by vacuum rotary evaporation, control the temperature at 79±1℃ and stir for 40min; dissolve the product in methanol, then precipitate with ether, filter and separate the precipitate, repeat the above dissolution → precipitation → filtration operation 3 times to obtain a polyamino polymer.

[0063] S1.2: According to the mass volume ratio of 1g:1g:9.1g:0.12g:0.79g:50mL, silica with particle size D90 of 15nm and 100nm, 1H,1H,2H,2H-perfluorodecyltriethoxysilane, KH-570 silane coupling agent, decyltrimethoxysilane, and 90% vol ethanol aqueous solution are taken for use; silica is added to the ethanol aqueous solution, ultrasonically dispersed for 30min, and then ammonia water is added to adjust the pH to 7.7, and then the three spare silane coupling agents are added thereto, the temperature is controlled at 52±0.5℃, and stirred for 6h; the product is centrifuged, and the separated precipitate is washed with ethanol and water in turn, and then dried to obtain fluorocarbon-based / acrylate-based composite modified silica.

[0064] S1.3: Take fluorocarbon-based / acrylate-based composite modified silica, polyamino polymer and methanol according to the mass volume ratio of 1g:0.06g:15mL; add fluorocarbon-based / acrylate-based composite modified silica to methanol, ultrasonically disperse it for 30 minutes, add polyamino polymer thereto, control the temperature at 50°C, and stir for 1.5 hours; centrifuge the product, wash the separated precipitate with water, and dry it to obtain modified silica.

[0065] S2: Anti-cracking coating:

[0066] S2.1: Epoxy resin E44 (solid content: 99 wt%) and 20% vol ethanol aqueous solution were mixed in a mass-to-volume ratio of 100 g:35 mL to obtain component A.

[0067] S2.2: Modified silica, triethylenetetramine, and 20% vol ethanol aqueous solution were mixed in a mass volume ratio of 25 g:3 g:30 mL to obtain component B.

[0068] S2.3: Expose the inner wall (including the side wall and bottom) of the liquid reservoir of the coverslip (without the specimen slide) to ultraviolet light with a wavelength of 254 nm for 20 minutes to obtain a pretreated coverslip.

[0069] S2.4: Take component A and component B in a mass ratio of 2:1, add component B to component A, mix well, and obtain an anti-cracking coating.

[0070] S2.5: Apply the anti-cracking coating to the inner wall (including the side wall and bottom) of the liquid reservoir in the pretreated cover sheet, control the temperature at 35°C, let it stand and cure for 2 hours, and then dry it naturally to obtain the anti-cracking cover sheet.

[0071] The anti-cracking cover sheet obtained in this example was tested for its hydrophobic and oleophobic properties. The results showed that the water contact angle of the coating surface on the inner wall of the liquid storage tank was 155°, and the soybean oil contact angle was 151°.

[0072] The anti-cracking cover sheet obtained in this example was used to perform an immunohistochemistry (IHC) experiment. The experimental steps are shown in Table 1 (the reagents involved in Table 1 are all conventional reagents in immunohistochemistry. The time "0" indicates the addition of the reagent, the waiting time is 0, and the next step is directly performed).

[0073] Table 1 Immunohistochemistry experimental steps

[0074]

[0075]

[0076] The components of the reagents mentioned in Table 1 are as follows:

[0077] IHC Dewax Solution: Alkane compound;

[0078] IHC Wash Solution: Trizma base, NaCl, distilled water;

[0079] Repair solution (IHC ER Solution 2): citric acid monohydrate, sodium citrate dihydrate, deionized water, glycerol, Tween-20; peroxide blocker (Peroxide Block): H2O2, PBS buffer;

[0080] Reaction Enhancer: Na2HPO4, KH2PO4, NaCl, KCl, distilled water.

[0081] After 50 times of use in immunohistochemistry experiments, the coverslips were Figure 1 As shown, no cracking and deformation occurred.

[0082] Example 2

[0083] The cover sheet with the liquid storage tank (the cover sheet structure and material are the same as those in Example 1) is subjected to anti-cracking treatment in the following steps:

[0084] S1: Preparation of modified silica:

[0085] S1.1: Take triethylenetetramine and methanol in a mass-to-volume ratio of 1g:0.8mL, mix them, place them in an ice bath, cool to 7°C, control the temperature at 2.5±1.5°C, take methyl acrylate with a mass of 1 / 4.24 of triethylenetetramine and add it dropwise. After the addition is complete, control the temperature at 27±1°C and stir for 4h; then remove the methanol by vacuum rotary evaporation, control the temperature at 76±1°C and stir for 45min; dissolve the product in methanol, then precipitate with ether, filter and separate the precipitate, repeat the above dissolution → precipitation → filtration operation 3 times to obtain a polyamino polymer.

[0086] S1.2: According to the mass volume ratio of 1g:1.5g:8.73g:0.14g:1.1g:50mL, silica with particle size D90 of 15nm and 100nm, 1H,1H,2H,2H-perfluorodecyltriethoxysilane, KH-570 silane coupling agent, decyltrimethoxysilane, and 90% vol ethanol aqueous solution are taken for use; silica is added to the ethanol aqueous solution, ultrasonically dispersed for 30min, and then ammonia water is added to adjust the pH to 7.8, and then the three spare silane coupling agents are added thereto, the temperature is controlled at 58±1℃, and stirred for 4h; the product is centrifuged, and the separated precipitate is washed with ethanol and water in turn, and then dried to obtain fluorocarbon-based / acrylate-based composite modified silica.

[0087] S1.3: Take fluorocarbon-based / acrylate-based composite modified silica, polyamino polymer and methanol according to the mass volume ratio of 1g:0.1g:20mL; add fluorocarbon-based / acrylate-based composite modified silica to methanol, ultrasonically disperse it for 30 minutes, add polyamino polymer thereto, control the temperature at 40°C, and stir for 2 hours; centrifuge the product, wash the separated precipitate with water, and dry it to obtain modified silica.

[0088] S2: Anti-cracking coating:

[0089] S2.1: Epoxy resin E44 (solid content: 99 wt%) and 20% vol ethanol aqueous solution were mixed in a mass volume ratio of 90 g:30 mL to obtain component A.

[0090] S2.2: Modified silica, triethylenetetramine, perfluorooctane, and 20% vol ethanol aqueous solution were mixed in a mass-to-volume ratio of 16 g:5 g:5 g:23 mL to obtain component B.

[0091] S2.3: Expose the inner wall (including the side wall and bottom) of the liquid reservoir of the cover slip (without the specimen slide) to ultraviolet light with a wavelength of 254 nm for 30 minutes to obtain a pretreated cover slip.

[0092] S2.4: Take component A and component B in a mass ratio of 2.5:1, add component B to component A, mix well, and obtain an anti-cracking coating.

[0093] S2.5: Apply the anti-cracking coating to the inner wall (including the side wall and bottom) of the liquid reservoir in the pretreated cover sheet, control the temperature at 30°C, let it stand and cure for 2.5 hours, and then dry it naturally to obtain the anti-cracking cover sheet.

[0094] The anti-cracking cover sheet obtained in this example was tested for its hydrophobic and oleophobic properties. The results showed that the water contact angle of the coating surface on the inner wall of the liquid storage tank was 152°, and the soybean oil contact angle was 150°.

[0095] Following the steps in Example 1, the anti-cracking cover sheet obtained in this example was used to perform immunohistochemical experiments. Figure 1 As shown, no cracking and deformation occurred.

[0096] Example 3

[0097] The cover sheet with the liquid storage tank (the cover sheet structure and material are the same as those in Example 1) is subjected to anti-cracking treatment in the following steps:

[0098] S1: Preparation of modified silica:

[0099] S1.1: Take triethylenetetramine and methanol in a mass-to-volume ratio of 1g:1mL, mix them and place them in an ice bath. After cooling to 7℃, control the temperature at 2.5±1.5℃, take methyl acrylate with a mass of 1 / 2.55 of triethylenetetramine and add it dropwise. After the addition is complete, control the temperature at 25.5±1℃ and stir for 4.5h; then remove the methanol by vacuum rotary evaporation, control the temperature at 73±1.5℃ and stir for 50min; dissolve the product in methanol, then precipitate with ether, filter and separate the precipitate, repeat the above dissolution → precipitation → filtration operation 3 times to obtain a polyamino polymer.

[0100] S1.2: According to the mass volume ratio of 1g:1.5g:6g:0.12g:1.3g:50mL, silica with particle size D90 of 15nm and 100nm, 1H,1H,2H,2H-perfluorodecyltriethoxysilane, KH-570 silane coupling agent, decyltrimethoxysilane, and 90% vol ethanol aqueous solution are taken for use; silica is added to the ethanol aqueous solution, ultrasonically dispersed for 30min, and then ammonia water is added to adjust the pH to 8.5, and then the three spare silane coupling agents are added thereto, the temperature is controlled at 55±1℃, and stirred for 5h; the product is centrifuged, and the separated precipitate is washed with ethanol and water in turn, and then dried to obtain fluorocarbon-based / acrylate-based composite modified silica.

[0101] S1.3: Take fluorocarbon-based / acrylate-based composite modified silica, polyamino polymer and methanol according to the mass volume ratio of 1g:0.08g:20mL; add fluorocarbon-based / acrylate-based composite modified silica to methanol, ultrasonically disperse for 30 minutes, add polyamino polymer thereto, control the temperature at 30°C, and stir for 2.5 hours; centrifuge the product, wash the separated precipitate with water, and dry it to obtain modified silica.

[0102] S2: Anti-cracking coating:

[0103] S2.1: Epoxy resin E44 (solid content: 99 wt%) and 20% vol ethanol aqueous solution were mixed in a mass-to-volume ratio of 80 g:25 mL to obtain component A.

[0104] S2.2: Modified silica, triethylenetetramine, perfluorooctane, and 20% vol ethanol aqueous solution were mixed in a mass volume ratio of 20 g:4 g:3 g:25 mL to obtain component B.

[0105] S2.3: Expose the inner wall (including the side wall and bottom) of the liquid reservoir of the cover slip (without the specimen slide) to ultraviolet light with a wavelength of 254 nm for 15 minutes to obtain a pretreated cover slip.

[0106] S2.4: Take component A and component B in a mass ratio of 3:1, add component B to component A, mix well, and obtain an anti-cracking coating.

[0107] S2.5: Apply the anti-cracking coating to the inner wall (including the side wall and bottom) of the liquid storage tank in the pretreated cover sheet, control the temperature at 40°C, let it stand and cure for 1.5 hours, and then dry it naturally to obtain the anti-cracking cover sheet.

[0108] The anti-cracking cover sheet obtained in this example was tested for its hydrophobic and oleophobic properties. The results showed that the water contact angle of the coating surface on the inner wall of the liquid storage tank was 156°, and the soybean oil contact angle was 153°.

[0109] Following the steps in Example 1, the anti-cracking cover sheet obtained in this example was used to perform immunohistochemical experiments. Figure 1 As shown, no cracking and deformation occurred.

[0110] Example 4

[0111] The cover sheet with a liquid storage tank (the cover sheet structure and material are the same as those in Example 1) is treated to prevent cracking. The only difference from Example 1 is that the polycondensation reaction time is shortened during the preparation of the polyamino polymer in step S1.1. The specific steps of this example are as follows: S1: Preparation of modified silica:

[0112] S1.1: Take triethylenetetramine and methanol in a mass-to-volume ratio of 1g:1mL, mix them and place them in an ice bath. After cooling to 7℃, control the temperature at 2.5±1.5℃, take methyl acrylate with a mass of 1 / 3 of triethylenetetramine and add it dropwise. After the addition is complete, control the temperature at 22±0.5℃ and stir for 5h; then remove the methanol by vacuum rotary evaporation, control the temperature at 79±1℃ and stir for 20min; dissolve the product in methanol, then precipitate with ether, filter and separate the precipitate, repeat the above dissolution → precipitation → filtration operation 3 times to obtain a polyamino polymer.

[0113] S1.2: According to the mass volume ratio of 1g:1g:9.1g:0.12g:0.79g:50mL, silica with particle size D90 of 15nm and 100nm, 1H,1H,2H,2H-perfluorodecyltriethoxysilane, KH-570 silane coupling agent, decyltrimethoxysilane, and 90% vol ethanol aqueous solution are taken for use; silica is added to the ethanol aqueous solution, ultrasonically dispersed for 30min, and then ammonia water is added to adjust the pH to 7.7, and then the three spare silane coupling agents are added thereto, the temperature is controlled at 52±0.5℃, and stirred for 6h; the product is centrifuged, and the separated precipitate is washed with ethanol and water in turn, and then dried to obtain fluorocarbon-based / acrylate-based composite modified silica.

[0114] S1.3: Take fluorocarbon-based / acrylate-based composite modified silica, polyamino polymer and methanol according to the mass volume ratio of 1g:0.06g:15mL; add fluorocarbon-based / acrylate-based composite modified silica to methanol, ultrasonically disperse it for 30 minutes, add polyamino polymer thereto, control the temperature at 50°C, and stir for 1.5 hours; centrifuge the product, wash the separated precipitate with water, and dry it to obtain modified silica.

[0115] S2: Anti-cracking coating:

[0116] S2.1: Epoxy resin E44 (solid content: 99 wt%) and 20% vol ethanol aqueous solution were mixed in a mass-to-volume ratio of 100 g:35 mL to obtain component A.

[0117] S2.2: Modified silica, triethylenetetramine, and 20% vol ethanol aqueous solution were mixed in a mass volume ratio of 25 g:3 g:30 mL to obtain component B.

[0118] S2.3: Expose the inner wall (including the side wall and bottom) of the liquid reservoir of the coverslip (without the specimen slide) to ultraviolet light with a wavelength of 254 nm for 20 minutes to obtain a pretreated coverslip.

[0119] S2.4: Take component A and component B in a mass ratio of 2:1, add component B to component A, mix well, and obtain an anti-cracking coating.

[0120] S2.5: Apply the anti-cracking coating to the inner wall (including the side wall and bottom) of the liquid reservoir in the pretreated cover sheet, control the temperature at 35°C, let it stand and cure for 2 hours, and then dry it naturally to obtain the anti-cracking cover sheet.

[0121] The anti-cracking cover sheet obtained in this example was tested for its hydrophobic and oleophobic properties. The results showed that the water contact angle of the coating surface on the inner wall of the liquid storage tank was 157°, and the soybean oil contact angle was 154°.

[0122] Following the steps in Example 1, the anti-cracking cover sheet obtained in this example was used to perform immunohistochemical experiments. Figure 2 As shown, there are a few cracks on both sides.

[0123] Analysis of the test results: Compared to Example 1, the water and oil contact angles of the coating surface in Example 4 increased, but the number of coverslips that could be used in immunohistochemistry experiments decreased. This suggests that, within a certain range, shortening the polycondensation reaction time during the preparation of the polyamino polymer can adversely affect the durability of the coverslip. This is presumably because a shorter polycondensation reaction time reduces the number of amino groups in the polyamino polymer molecules, reducing the bonding strength of the modified silica to the coverslip and thus affecting the durability of the coverslip.

[0124] Example 5

[0125] The cover sheet with a liquid storage tank (the cover sheet structure and material are the same as those in Example 1) is treated to prevent cracking. The only difference from Example 3 is that the polycondensation reaction time is extended during the preparation of the polyamino polymer in step S1.1. The specific steps of this example are as follows: S1: Preparation of modified silica:

[0126] S1.1: Take triethylenetetramine and methanol in a mass-to-volume ratio of 1g:1mL, mix them and place them in an ice bath. After cooling to 7℃, control the temperature at 2.5±1.5℃, take methyl acrylate with a mass of 1 / 2.55 of triethylenetetramine and add it dropwise. After the addition is complete, control the temperature at 25.5±1℃ and stir for 4.5h; then remove the methanol by vacuum rotary evaporation, control the temperature at 73±1.5℃ and stir for 1.5h; dissolve the product in methanol, then precipitate with ether, filter and separate the precipitate, repeat the above dissolution → precipitation → filtration operation 3 times to obtain a polyamino polymer.

[0127] S1.2: According to the mass volume ratio of 1g:1.5g:6g:0.12g:1.3g:50mL, silica with particle size D90 of 15nm and 100nm, 1H,1H,2H,2H-perfluorodecyltriethoxysilane, KH-570 silane coupling agent, decyltrimethoxysilane, and 90% vol ethanol aqueous solution are taken for use; silica is added to the ethanol aqueous solution, ultrasonically dispersed for 30min, and then ammonia water is added to adjust the pH to 8.5, and then the three spare silane coupling agents are added thereto, the temperature is controlled at 55±1℃, and stirred for 5h; the product is centrifuged, and the separated precipitate is washed with ethanol and water in turn, and then dried to obtain fluorocarbon-based / acrylate-based composite modified silica.

[0128] S1.3: Take fluorocarbon-based / acrylate-based composite modified silica, polyamino polymer and methanol according to the mass volume ratio of 1g:0.08g:20mL; add fluorocarbon-based / acrylate-based composite modified silica to methanol, ultrasonically disperse for 30 minutes, add polyamino polymer thereto, control the temperature at 30°C, and stir for 2.5 hours; centrifuge the product, wash the separated precipitate with water, and dry it to obtain modified silica.

[0129] S2: Anti-cracking coating:

[0130] S2.1: Epoxy resin E44 (solid content: 99 wt%) and 20% vol ethanol aqueous solution were mixed in a mass-to-volume ratio of 80 g:25 mL to obtain component A.

[0131] S2.2: Modified silica, triethylenetetramine, perfluorooctane, and 20% vol ethanol aqueous solution were mixed in a mass volume ratio of 20 g:4 g:3 g:25 mL to obtain component B.

[0132] S2.3: Expose the inner wall (including the side wall and bottom) of the liquid reservoir of the cover slip (without the specimen slide) to ultraviolet light with a wavelength of 254 nm for 15 minutes to obtain a pretreated cover slip.

[0133] S2.4: Take component A and component B in a mass ratio of 3:1, add component B to component A, mix well, and obtain an anti-cracking coating.

[0134] S2.5: Apply the anti-cracking coating to the inner wall (including the side wall and bottom) of the liquid storage tank in the pretreated cover sheet, control the temperature at 40°C, let it stand and cure for 1.5 hours, and then dry it naturally to obtain the anti-cracking cover sheet.

[0135] The anti-cracking cover sheet obtained in this example was tested for its hydrophobic and oleophobic properties. The results showed that the water contact angle of the coating surface on the inner wall of the liquid storage tank was 149°, and the soybean oil contact angle was 140°.

[0136] Following the steps in Example 1, the anti-cracking cover sheet obtained in this example was used to perform immunohistochemical experiments. Figure 3 As shown, there are a few cracks on both sides.

[0137] Analysis of the test results: Compared to Example 3, the water and oil contact angles of the coating surface in Example 5 were reduced, and the number of times the coverslip could be used in immunohistochemistry experiments was reduced. This indicates that, within a certain range, extending the polycondensation reaction time during the preparation of the polyamino polymer can adversely affect the durability of the coverslip. This is presumably because a longer polycondensation reaction time results in larger polyamino polymer molecules, which can easily damage the hydrophobic and oleophobic layer on the modified silica surface, reducing the hydrophobic and oleophobic properties of the coating and, in turn, affecting the durability of the coverslip.

[0138] Comparative Example 1

[0139] This comparative example is a cover sheet with a liquid storage tank (the cover sheet structure and material are the same as in Example 1), and no anti-cracking treatment is performed.

[0140] Following the steps in Example 1, the coverslips in this comparative example were used for immunohistochemical experiments. Figure 4 As shown, there is severe cracking.

[0141] Analysis of test results: Compared with Comparative Example 1, the number of times the cover sheet can be used without histochemical experiments after the anti-cracking treatment of Examples 1 to 3 is significantly increased, indicating that its durability has been effectively improved. It is speculated that the reason is that when the anti-cracking coating is used to form a coating on the inner wall of the cover sheet liquid reservoir in Examples 1 to 3, while exerting a physical barrier effect, it can also utilize its hydrophobic and oleophobic properties to reduce the penetration of organic solutions, thereby reducing the contact between the organic solution and the cover sheet. In addition, the hydrophobic and oleophobic properties of the coating can also repel small molecules such as plasticizers. Under the above combined effects, the dissolution of small molecules such as plasticizers in the cover sheet can be slowed down, thereby improving the durability of the cover sheet and slowing down the cracking or deformation of the cover sheet.

[0142] Comparative Example 2

[0143] The cover sheet with a liquid reservoir (the cover sheet structure and material are the same as in Example 1) was subjected to anti-cracking treatment. The only difference from Example 1 is that the polyamino polymer is not grafted onto the surface of the silica, that is, steps S1.1 and S1.3 are not performed. The specific steps of this comparative example are as follows:

[0144] S1: Preparation of modified silica:

[0145] According to the mass-to-volume ratio of 1g:1g:9.1g:0.12g:0.79g:50mL, silica with a particle size D90 of 15nm and 100nm, 1H,1H,2H,2H-perfluorodecyltriethoxysilane, KH-570 silane coupling agent, decyltrimethoxysilane, and 90% vol ethanol aqueous solution were taken for later use; silica was added to the ethanol aqueous solution, ultrasonically dispersed for 30 minutes, and then ammonia water was added to adjust the pH to 7.7. The three reserved silane coupling agents were then added thereto, the temperature was controlled at 52±0.5°C, and stirred for 6 hours; the product was centrifuged, and the separated precipitate was washed with ethanol and water in sequence, and then dried to obtain modified silica.

[0146] S2: Anti-cracking coating:

[0147] S2.1: Epoxy resin E44 (solid content: 99 wt%) and 20% vol ethanol aqueous solution were mixed in a mass-to-volume ratio of 100 g:35 mL to obtain component A.

[0148] S2.2: Modified silica, triethylenetetramine, and 20% vol ethanol aqueous solution were mixed in a mass volume ratio of 25 g:3 g:30 mL to obtain component B.

[0149] S2.3: Expose the inner wall (including the side wall and bottom) of the liquid reservoir of the coverslip (without the specimen slide) to ultraviolet light with a wavelength of 254 nm for 20 minutes to obtain a pretreated coverslip.

[0150] S2.4: Take component A and component B in a mass ratio of 2:1, add component B to component A, mix well, and obtain an anti-cracking coating.

[0151] S2.5: Apply the anti-cracking coating to the inner wall (including the side wall and bottom) of the liquid reservoir in the pretreated cover sheet, control the temperature at 35°C, let it stand and cure for 2 hours, and then dry it naturally to obtain the anti-cracking cover sheet.

[0152] The anti-cracking cover sheet obtained in this comparative example was tested for its hydrophobic and oleophobic properties, and the water contact angle of the coating surface on the inner wall of the liquid storage tank was measured to be 160°, and the soybean oil contact angle was 158°.

[0153] Following the steps in Example 1, the anti-cracking cover sheet obtained in this comparative example was used to perform immunohistochemical experiments. Figure 5 As shown, there is severe cracking.

[0154] Analysis of the test results: Compared with Example 1, the water contact angle and oil contact angle of the coating surface in Comparative Example 2 increased, but the number of times the cover slip could be used for immunohistochemistry experiments decreased, indicating that by grafting a polyamino polymer on the surface of silica, the durability of the cover slip can be improved. It is speculated that the reason is that during the curing process of the coating, the amino groups in the polyamino polymer can react with the epoxy groups in the epoxy resin, forming a covalent bond between the modified silica and the epoxy resin; and when the coating is applied, the amino groups in the polyamino polymer can bind to the carboxyl groups on the inner wall surface of the reservoir through electrostatic attraction and hydrogen bonding. In this way, the bonding strength between the epoxy resin and the modified silica on the cover slip surface can be improved, making the modified silica less likely to fall off and the coating less likely to be damaged, thereby greatly improving the durability of the cover slip.

[0155] Comparative Example 3

[0156] A cover sheet with a liquid reservoir (the cover sheet structure and material are the same as in Example 1) was treated to prevent cracking. The only difference from Example 1 is that the polyamino polymer grafted onto the surface of the silica was replaced with γ-aminopropyltriethoxysilane (KH-550). The specific steps of this comparative example are as follows:

[0157] S1: Preparation of modified silica:

[0158] According to the mass-to-volume ratio of 1g:1g:9.1g:1.5g:0.79g:50mL, silica with a particle size D90 of 15nm and 100nm, 1H,1H,2H,2H-perfluorodecyltriethoxysilane, KH-550 silane coupling agent, decyltrimethoxysilane, and 90% vol ethanol aqueous solution were taken for later use; silica was added to the ethanol aqueous solution, ultrasonically dispersed for 30 minutes, and then ammonia water was added to adjust the pH to 7.7. The three reserved silane coupling agents were then added thereto, the temperature was controlled at 52±0.5°C, and stirred for 6 hours; the product was centrifuged, and the separated precipitate was washed with ethanol and water in sequence, and then dried to obtain modified silica.

[0159] S2: Anti-cracking coating:

[0160] S2.1: Epoxy resin E44 (solid content: 99 wt%) and 20% vol ethanol aqueous solution were mixed in a mass-to-volume ratio of 100 g:35 mL to obtain component A.

[0161] S2.2: Modified silica, triethylenetetramine, and 20% vol ethanol aqueous solution were mixed in a mass volume ratio of 25 g:3 g:30 mL to obtain component B.

[0162] S2.3: Expose the inner wall (including the side wall and bottom) of the liquid reservoir of the coverslip (without the specimen slide) to ultraviolet light with a wavelength of 254 nm for 20 minutes to obtain a pretreated coverslip.

[0163] S2.4: Take component A and component B in a mass ratio of 2:1, add component B to component A, mix well, and obtain an anti-cracking coating.

[0164] S2.5: Apply the anti-cracking coating to the inner wall (including the side wall and bottom) of the liquid reservoir in the pretreated cover sheet, control the temperature at 35°C, let it stand and cure for 2 hours, and then dry it naturally to obtain the anti-cracking cover sheet.

[0165] The anti-cracking cover sheet obtained in this example was tested for its hydrophobic and oleophobic properties. The results showed that the water contact angle of the coating surface on the inner wall of the liquid storage tank was 137°, and the soybean oil contact angle was 129°.

[0166] Following the steps in Example 1, the anti-cracking cover sheet obtained in this example was used to perform immunohistochemical experiments. Figure 6 As shown, there are many cracks on both sides.

[0167] Analysis of the test results: Compared to Example 1, the water and oil contact angles of the coating surface in Comparative Example 3 were reduced, and the number of times the coverslip could be used in immunohistochemistry experiments was reduced. This indicates that compared to grafting small molecules with a small amount of amino groups onto the silica surface, grafting a polyamino polymer can significantly improve the durability of the coverslip. This is presumably because the polyamino polymer ensures the bonding strength of the modified silica to the coverslip while concentrating the distribution of amino groups on the silica surface. This reduces masking and damage to the fluorocarbon-based hydrophobic and oleophobic layer, and improves the coating's effectiveness in slowing the dissolution of small molecules such as plasticizers from the coverslip.

[0168] Unless otherwise specified, the raw materials and equipment used in the present invention are commonly used in the art; the methods used in the present invention are conventional methods in the art unless otherwise specified.

[0169] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent transformation made to the above embodiment based on the technical essence of the present invention still fall within the scope of protection of the technical solution of the present invention.

Claims

1. An application of an anti-cracking coating in slowing down cracking of a cover sheet with a liquid storage tank, characterized in that: The anti-cracking coating comprises component A and component B; component A comprises epoxy resin; component B comprises modified SiO2; before the anti-cracking coating is applied to the inner wall of the liquid reservoir of the cover plate, the inner wall of the liquid reservoir is pretreated to form carboxyl groups on the surface of the inner wall of the liquid reservoir; the modified SiO2 is SiO2 with a fluorocarbon-based hydrophobic and oleophobic layer and a polyamino polymer grafted on the surface: the polyamino polymer is obtained by polymerization reaction using triethylenetetramine and methyl acrylate as monomers; a silane coupling agent is grafted on the surface of the SiO2 to obtain a fluorocarbon-based / acrylate-based composite modified SiO2, and the silane coupling agent includes a fluorocarbon-based silane coupling agent and an acrylate silane coupling agent; the polyamino polymer is grafted onto the fluorocarbon-based / acrylate-based composite modified SiO2 by utilizing the addition reaction between the amino group and the acrylate group to obtain the modified SiO2.

2. The use according to claim 1, wherein The component A is calculated in parts by weight The invention comprises the following components: 80-100 parts of epoxy resin and 23-35 parts of solvent A; the component B comprises the following components in parts by weight: 16-25 parts of modified SiO2, 3-5 parts of amine curing agent, 0-5 parts of compound containing amino group and perfluoro group, and 20-30 parts of solvent B; the mass ratio of the component A to the component B is 2-3:

1.

3. The use according to claim 1, characterized in that The process for preparing the polyamino polymer specifically includes the following steps: mixing triethylenetetramine and solvent I, cooling the mixture to 0-7°C, adding methyl acrylate dropwise thereto, and then reacting at 20-30°C for 4-5 hours; removing solvent I, and reacting at 70-80°C for 40-50 minutes to obtain the polyamino polymer.

4. The use according to claim 1, wherein The process of preparing fluorocarbon-based / acrylate-based composite modified SiO2 specifically includes the following steps: dispersing SiO2 in solvent II, adjusting the pH to 7.5-8.5, adding a silane coupling agent, reacting at 50-60°C for 4-6 hours, separating the product, and obtaining fluorocarbon-based / acrylate-based composite modified SiO2.

5. The use according to claim 1 or 4, characterized in that The silane coupling agent includes a fluorocarbon-based silane coupling agent, an acrylate silane coupling agent and an alkyl silane coupling agent in a molar ratio of 1:0.03-0.05:0-0.3; the mass ratio of the SiO2 to the silane coupling agent is 1:3-5.

6. The use according to claim 5, characterized in that The fluorocarbon-based silane coupling agent is 1H,1H,2H,2H-perfluorodecyltriethoxysilane; the acrylate silane coupling agent is one or more of 3-(methacryloyloxy)propyltrimethoxysilane, 3-(acryloyloxy)propyltrimethoxysilane and 3-(methacryloyloxy)propyltriethoxysilane; in the alkyl silane coupling agent, the number of carbon atoms in the alkyl chain is 8 to 10.

7. The use according to claim 1, wherein The process of preparing modified SiO2 from a polyamino polymer and a fluorocarbon / acrylate composite modified SiO2 specifically includes the following steps: dispersing the fluorocarbon / acrylate composite modified SiO2 in solvent III, adding the polyamino polymer, and reacting at 30-50°C for 1.5-2.5h to obtain modified SiO2.

8. The use according to claim 1, wherein The cover plate is made of polycarbonate.

9. The use according to claim 8, characterized in that The pretreatment method is to irradiate with ultraviolet light having a wavelength of 200-275 nm.

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