A development and strengthening agent, its preparation method, and its application in preventing defects in dry plate glass film.

Abstract

This invention belongs to the technical field of film reinforcement agents, specifically relating to a developing reinforcement agent, its preparation method, and its application in dry-plate glass films. The developing reinforcement agent is made from alkaline gelatin, Kathon, waterborne epoxy resin, and water; the mass ratio of the alkaline gelatin, Kathon, waterborne epoxy resin, and water is 3–9:0.1–0.3:0.1–0.6:91–97. This invention uses alkaline gelatin, waterborne epoxy resin, and Kathon to form a developing reinforcement agent, which exhibits good stability and significantly slows down the degradation rate of the emulsion layer. When used in dry-plate glass films, the developing reinforcement agent also has a reinforcing effect, preventing defects in the dry-plate glass films.

Description

Technical Field

[0001] This invention belongs to the field of film reinforcement technology, and relates to a development reinforcement agent, its preparation method, and its application in dry plate glass films. Background Technology

[0002] Glass negatives are a major invention by humankind, preserving authentic images of objects based on scientific research. For example, glass negatives of ancient architecture are of great value to research on Chinese history, the history of the Palace Museum, the restoration of ancient buildings to their original state, and the protection and restoration of ancient buildings. They possess the dual attributes of being a carrier of historical images and a 20th-century artifact. However, due to the characteristics of the photosensitive material and the storage environment, glass negative archives suffer from a variety of serious and self-destructive defects, such as image deterioration, cracking, warping, breakage into fragments, blurring or disappearance, or the appearance of a silvering effect. All of these defects cause incalculable loss of the image information on the negative.

[0003] Dry plate glass film, whose emulsion layer is mainly made of gelatin, is a collagen-based water-soluble biopolymer extracted from the connective tissue of vertebrates. During long-term storage, dry plate glass film may suffer from cracking, warping, and peeling. These problems are mainly caused by the long-term exposure of gelatin to climatic changes, which damages the structural characteristics of its protein chains—the triple helix structure—leading to a decline in its physical and mechanical properties. After the gelatin loses its adhesiveness, its adhesion weakens, and it shrinks. However, the shrinkage rate is very different from that of the dry plate glass, causing the gelatin photosensitive film to detach from the dry plate glass.

[0004] Based on a review of relevant literature, and considering the fragility of the film emulsion layer, which is prone to peeling, crumbling, cracking, and peeling, scholar Du Qingping, in his article "Further Discussion on the Protection of Microfilm Archives," analyzed the properties of gelatin in the film emulsion layer. Based on these properties, he proposed relevant measures for the protection of microfilm and several issues that need attention during preservation.

[0005] 1. The temperature and humidity of the film storage environment should be relatively stable, with temperature changes not exceeding ±2℃ and relative humidity changes not exceeding ±5% within 24 hours. The air introduced into the film storage should also be purified. Although this method can slow down the degradation rate and time of the film emulsion layer, it cannot solve the problem of emulsion layer degradation from the source mechanism. It also requires strict control of the temperature and humidity of the storage environment. The environmental temperature and humidity requirements are stringent, and once the temperature changes significantly, there is a problem of poor stability.

[0006] 2. Protective treatments can be applied to the above-mentioned defects using hydrochloric acid, glacial acetic acid, anhydrous ethanol, or sodium carbonate. However, extensive experiments have shown that high concentrations of alcohols can cause significant shrinkage of the emulsion film on the glass film, while acids can accelerate the degradation of the already cracked, peeling, and flaking emulsion layer, causing deep damage to the glass film. Summary of the Invention

[0007] In view of the technical problems of the harsh conditions and deep damage to the glass film caused by the existing dry plate glass film processing, the present invention provides a development and strengthening agent, a preparation method and its application in dry plate glass film.

[0008] This invention uses alkaline gelatin, water-based epoxy resin, and Kathon to form a developing and reinforcing agent. It has good stability and significantly slows down the degradation rate of the emulsion layer. When the developing and reinforcing agent is used in dry glass film, it also has a reinforcing effect and plays a role in preventing defects in dry glass film.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0010] A development and strengthening agent is made from alkaline gelatin, Kathon, waterborne epoxy resin and water; wherein the mass ratio of alkaline gelatin, Kathon, waterborne epoxy resin and water is 3-9:0.1-0.3:0.1-0.6:91-97.

[0011] Further specified, the mass ratio of the alkaline gelatin, Kathon, waterborne epoxy resin and water is 6:0.2:0.5:94.

[0012] Furthermore, the enhancement agent exhibits diffraction peaks at both 2θ = 8° and 2θ = 44°.

[0013] Further specified, the enhancement agent has a Zeta potential of -36.33 mV and an average viscosity of 177.65 mm. 2 / S.

[0014] The preparation method of the enhancement agent as described includes the following steps:

[0015] S1. Prepare alkaline gelatin, Kathon, water-based epoxy resin and water according to the stated amounts;

[0016] S2. Dissolve the alkaline gelatin in water and heat it to 45℃~55℃, stirring until a mixed solution is obtained;

[0017] S3. Add Kathon and water-based epoxy resin sequentially to the mixed solution in step S2, mix evenly, and the preparation is complete.

[0018] The application of the described strengthening agent in preventing defects in dry plate glass film.

[0019] Further defining the application, the application is as follows: the developing and reinforcing agent is evenly applied to the surface of the dry glass film, and the film is placed horizontally for 48h to 72h to develop and reinforce the dry glass film, thereby completing the prevention of defects in the dry glass film.

[0020] Furthermore, the development and strengthening agent can reduce the degradation rate of gelatin on the dry plate glass substrate.

[0021] Furthermore, the development and strengthening agent can improve the mechanical strength and light transmittance of the dry plate glass substrate surface, and reduce the reflectivity of the dry plate glass substrate surface.

[0022] Further specifying, defects in dry-plate glass film include cracking, warping, peeling, and / or powdering.

[0023] Compared with the prior art, the beneficial effects of the present invention are:

[0024] 1. This invention uses alkaline gelatin, water-based epoxy resin, and Kathon as the main raw materials to form a developing and reinforcing agent that can be compatible with cross-linking, toughening, and strengthening effects. When developing and reinforcing dry glass substrates, the requirements for ambient temperature and humidity are relatively low, which effectively improves the aging resistance of dry glass substrates. The developing and reinforcing agent can significantly slow down the degradation rate of dry glass substrates and avoid the occurrence of defects such as cracking, peeling, flaking, and / or powdering of the emulsion layer on the dry glass substrates, thereby playing a preventive role for dry glass substrates.

[0025] 2. The developing and reinforcing agent provided by this invention, through the combined action of alkaline gelatin, waterborne epoxy resin, and Kathon, exhibits diffraction peaks at both 2θ = 8° and 2θ = 44°. Therefore, it does not significantly alter the phase and crystal structure of elemental silver on the surface of the dry plate glass film. Furthermore, it increases the content of the triple helix structure of gelatin within the photosensitive film on the dry plate glass film, thereby improving and optimizing the physical and chemical properties of the dry plate glass film from the source.

[0026] 3. The development and strengthening agent provided by this invention has a Zeta potential of -36.33mV, indicating that the addition of Kathon greatly improves the dispersion performance of the solute within the development and strengthening agent, making the development and strengthening agent system more stable; the average viscosity is 177.65mV. 2 The / S indicates that using alkaline gelatin can improve the adhesion of the development and strengthening agent, helping it to better fill and repair scratches and small pores on the surface of the disease. Therefore, the present invention utilizes alkaline gelatin, Kathon, and water-based epoxy resin in combination to achieve a better protective effect against the disease.

[0027] 4. Through experimental verification, the pH and water resistance of the film are improved, further demonstrating that the aging resistance of the dry plate glass film is effectively improved. In addition, after accelerated aging of the dry plate glass film, the degradation rate of the developed and reinforced dry plate glass film is significantly slowed down, thereby avoiding deep damage to the dry plate glass film caused by the developing and reinforcing agent.

[0028] 5. The development and strengthening agent provided by the present invention can fill the gaps caused by scratches, and in the visible light range, it can improve the light transmittance of the dry plate glass film surface and reduce the reflectivity of the dry plate glass film surface. This not only helps to distinguish the image information carried by the dry plate glass film itself, but also does not affect the display of the dry plate glass film image. At the same time, it eliminates some light reflection, thereby avoiding the mirror phenomenon from affecting the imaging effect of the dry plate glass film.

[0029] 6. The development and strengthening agent provided by this invention can quickly form a transparent protective film with good adhesion on the dry plate glass film during development and strengthening, thereby improving the mechanical strength of the film surface. It also has low haze, ensuring that the image clarity is not affected during strengthening, and exhibits good anti-aging properties, preventing damage to the image information of the dry plate glass film after long-term storage. Furthermore, the film formed by the development and strengthening agent of this invention after being coated on the dry plate glass film has a larger contact angle and better hydrophobicity, effectively preventing damage to the dry plate glass film from moisture and pollutants in the environment, thus better achieving the strengthening and protection effect on the dry plate glass film. Attached Figure Description

[0030] Figure 1 A statistical graph of pH values ​​for different photosensitive films;

[0031] Figure 2 Viscosity statistics of development and strengthening agents made from acid-processed and alkali-processed gelatin;

[0032] Figure 3 Zeta potentials of the strengthening agent were compared between those with and without Kathon.

[0033] Figure 4 X-ray diffraction patterns of photosensitive films before and after coating with different developing and reinforcing agents;

[0034] Figure 5 TG / DTG curves of photosensitive films before and after coating with different development and hardening agents;

[0035] Figure 6 Transmittance and reflectance curves of photosensitive films before and after coating with different developing and reinforcing agents;

[0036] Figure 7 The surface morphology of the photosensitive film before and after coating with different development and reinforcement agents;

[0037] Figure 8 The graph shows the change in in vitro pH value of the photosensitive film over time before and after coating with different development and reinforcement agents;

[0038] Figure 9 Schematic diagram for determining the adhesion rating of paint film using a circular scratch test.

[0039] Figure 10The results of the paint film adhesion test (circle scratch test);

[0040] Figure 11 The haze test results of the reinforcing agent film after damp heat aging are shown for each embodiment;

[0041] Figure 12 The contact angle test results of the reinforcing agent film after damp heat aging are shown for each embodiment. Detailed Implementation

[0042] The technical solutions protected by this invention will now be described in detail with reference to the accompanying drawings and embodiments. However, it is obvious that the described embodiments are only some, not all, of the embodiments described herein. All other embodiments obtained by those skilled in the art based on the described embodiments without creative effort are within the scope of protection of this application.

[0043] The purpose of this invention is to develop and reinforce dry glass film by using alkaline gelatin, water-based epoxy resin and Kathon as the main raw materials to form a development and reinforcement agent that can be compatible with cross-linking, toughening and reinforcement effects, and to prevent the occurrence of defects such as warping, peeling and powdering of the emulsion layer of dry glass film.

[0044] The development and strengthening agent provided by the present invention is made of alkaline gelatin, Kathon, waterborne epoxy resin and water; the mass ratio of alkaline gelatin, Kathon, waterborne epoxy resin and water is 3-9:0.1-0.3:0.1-0.6:91-97.

[0045] In this invention, the mass fraction of alkali gelatin is 3% to 9% of the total mass of alkali gelatin and water.

[0046] Preferably, the mass ratio of alkaline gelatin, Kathon, waterborne epoxy resin and water is 6:0.2:0.5:94.

[0047] The present invention provides a method for preparing a surface-enhancing agent, comprising the following steps:

[0048] S1. Prepare alkaline gelatin, Kathon, water-based epoxy resin and water according to the stated amounts;

[0049] S2. Dissolve the alkaline gelatin in water and heat it to 45℃~55℃, stirring until a mixed solution is obtained;

[0050] S3. Add Kathon and water-based epoxy resin sequentially to the mixed solution in step S2, mix evenly, and the preparation is complete.

[0051] The development and strengthening agent provided by this invention has good stability, can reduce the degradation rate of gelatin on dry glass substrates, improve the mechanical strength and light transmittance of the dry glass substrate surface, and reduce the reflectivity of the dry glass substrate surface, thereby preventing dry glass substrate defects (cracking, warping and / or detachment).

[0052] The following specific examples illustrate the development and strengthening agent and its properties provided by the present invention.

[0053] It should be noted that the raw materials used in the following embodiments are as follows.

[0054] Alkali gelatin, Shanghai Maclean Biochemical Technology Co., Ltd.; Kathon (main components are 5-chloro-methyl-4-isothiazolinone and 2-methyl-4-isothiazolin-3-one), Guangzhou Zhongwan New Materials Co., Ltd.; Ammonium bromide, Chengdu Jiaye Biotechnology Co., Ltd.; Potassium iodide, Shanghai Zhanyun Chemical Co., Ltd.; Silver nitrate, Xilong Scientific Co., Ltd.; Waterborne epoxy resin B63; Ultrapure water; Concentrated ammonia, Wuhan Jiyesheng Chemical Co., Ltd.

[0055] It should be noted that the instruments used in the following embodiments are shown in Table 1.

[0056] Table 1. List of Instruments

[0057] Instrument Name model Manufacturer Electronic balance HX3002T Cixi Tiandong Weighing Instrument Factory Ultrapure water system WP-UP-WF-40 Sichuan Wotel Water Treatment Equipment Co., Ltd. Digital display constant temperature magnetic stirrer 85-2 Hangzhou Instrument & Motor Co., Ltd. Humid heat aging chamber HCP Memert (Shanghai) Trading Co., Ltd. Desktop Coating Viscometer with Four Cups LND-1A Shanghai Qigong Instrument Equipment Co., Ltd. Laser particle size Zeta potential meter S2107857 Brookhaven Instruments High-resolution X-ray diffractometer Smart Lab(9) Japanese Rika Co., Ltd. Thermal analyzer STA449F5 Netzsch Instruments GmbH, Germany Tungsten filament scanning electron microscope SU3500 Hitachi High Technology Company Ultraviolet-Near Infrared Spectrophotometer UV-lambda950 Platinum Elmer, Inc. pH meter S210 Mettler Toledo Instruments (Shanghai) Co., Ltd. Electric adhesion tester QFD Dongguan Dalai Instrument Co., Ltd. Haze meter TH-110 Hangzhou Caipu Technology Co., Ltd. Optical contact angle tester KRUSS-DSA100 German KRUSS

[0058] Example 1

[0059] The development and strengthening agent provided in this embodiment is made of alkaline gelatin, Kathon, waterborne epoxy resin and water.

[0060] The waterborne epoxy resin is waterborne epoxy resin B63; the water is ultrapure water.

[0061] This embodiment demonstrates the preparation method of the reinforcing agent as follows:

[0062] S1. Weigh 3g of alkaline gelatin and dissolve it in 97ml of ultrapure water. Then, place the solution in a magnetic stirrer and heat it in a constant temperature water bath at 45℃ until the alkaline gelatin is completely dissolved, obtaining a mixed solution. The mass fraction of alkaline gelatin in the mixed solution is 3%.

[0063] S2. Add 0.2g of Kathon and 0.5g of waterborne epoxy resin to the mixed solution in sequence to obtain the reinforcing agent.

[0064] Example 2

[0065] The development and strengthening agent provided in this embodiment is made of alkaline gelatin, Kathon, waterborne epoxy resin and water.

[0066] This embodiment demonstrates the preparation method of the reinforcing agent as follows:

[0067] S1. Weigh 6g of alkaline gelatin and dissolve it in 94ml of ultrapure water. Then, place the solution in a magnetic stirrer and heat it in a constant temperature water bath at 45℃ until the alkaline gelatin is completely dissolved, obtaining a mixed solution. The mass fraction of alkaline gelatin in the mixed solution is 6%.

[0068] S2. Add 0.2g of Kathon and 0.5g of waterborne epoxy resin to the mixed solution in sequence to obtain the reinforcing agent.

[0069] Example 3

[0070] The development and strengthening agent provided in this embodiment is made of alkaline gelatin, Kathon, waterborne epoxy resin and water.

[0071] This embodiment demonstrates the preparation method of the reinforcing agent as follows:

[0072] S1. Weigh 9g of alkaline gelatin and dissolve it in 91ml of ultrapure water. Then, place the solution in a magnetic stirrer and heat it in a constant temperature water bath at 45℃ until the alkaline gelatin is completely dissolved, obtaining a mixed solution. The mass fraction of alkaline gelatin in the mixed solution is 9%.

[0073] S2. Add 0.2g of Kathon and 0.5g of waterborne epoxy resin to the mixed solution in sequence to obtain the reinforcing agent.

[0074] Example 4

[0075] This embodiment uses the development and strengthening agent obtained from any one of the embodiments 1 to 3 to develop and strengthen a dry plate glass film.

[0076] The visualization and reinforcement method provided in this embodiment is as follows:

[0077] The development and strengthening agent is evenly applied to the surface of the dry plate glass film. Then, the dry plate glass film is placed horizontally on a flat table and left to stand for 48h to 72h. The dry plate glass film coated with the development and strengthening agent is obtained, thus completing the development and strengthening of the dry plate glass film.

[0078] In this embodiment, it is preferable to allow the substrate to stand for 72 hours. During coating, since the reinforcing agent exhibits good leveling properties, it should be allowed to flow completely across the surface of the film, ensuring complete coverage. Preferably, 4 ml of reinforcing agent is applied to every 100 square centimeters of dry glass film.

[0079] In this embodiment, the dry plate glass film is prepared by the following method.

[0080] Prepare a solution of 1 mol / L silver nitrate (using dilute ammonia), 1 mol / L ammonium chloride, 1 mol / L potassium iodide, and 15% gelatin. Add 10 mL of ammonium chloride and 0.5 mL of potassium iodide solution to the gelatin solution. Under light-protected conditions, slowly add 10 mL of silver nitrate solution dropwise to the boiling gelatin solution. After cooling, refrigerate overnight. The next day, remove the slides and rinse repeatedly with distilled water until all halides are removed. Reheat the emulsion; the photographic emulsion preparation is now complete. Apply the emulsion evenly to a smooth, warm glass plate within 25 hours. After drying, an unexposed glass negative is obtained. Place the unexposed glass negative in a perforated black box, find the appropriate exposure time, and take simple photographs. Finally, develop, stop developing, fix, and wash the photographed negatives; the dry glass plate negative is now complete.

[0081] The above describes several preferred groups of development and strengthening agents of the present invention and their application in development and strengthening on dry plate glass films. In order to verify the performance of the development and strengthening agents of the present invention and their application effect in preventing defects in dry plate glass films, the following test verification was conducted; at the same time, in order to highlight the advantages of the present invention, the following comparative examples were designed.

[0082] Comparative Example 1

[0083] The development and strengthening agent provided in this comparative example is made from acid-processed gelatin, Kathon, waterborne epoxy resin and water.

[0084] The comparative example demonstrates the preparation method of the reinforcing agent as follows:

[0085] S1. Weigh 6g of acid gelatin and dissolve it in 94ml of ultrapure water. Then place it in a magnetic stirrer and heat it in a constant temperature water bath. Set the temperature of the magnetic stirrer to 45℃ and stir until the alkaline gelatin is completely dissolved to obtain a mixed solution.

[0086] S2. Add 0.2g of Kathon and 0.5g of waterborne epoxy resin to the mixed solution in sequence to obtain the reinforcing agent.

[0087] Comparative Example 2

[0088] The development and strengthening agent provided in this comparative example is made from acid-processed gelatin, water-based epoxy resin, and water.

[0089] The comparative example demonstrates the preparation method of the reinforcing agent as follows:

[0090] S1. Weigh 6g of acid gelatin and dissolve it in 94ml of ultrapure water. Then place it in a magnetic stirrer and heat it in a constant temperature water bath. Set the temperature of the magnetic stirrer to 45℃ and stir until the alkaline gelatin is completely dissolved to obtain a mixed solution.

[0091] S2. Add 0.5g of water-based epoxy resin to the mixed solution to create a reinforcing agent.

[0092] Experiment 1: Performance Comparison of Different Gelatin Raw Materials

[0093] This experiment mainly involves analyzing and testing the pH and viscosity of development and strengthening agents formed from different gelatin raw materials.

[0094] 1. pH analysis

[0095] Test samples: blank photosensitive film (photosensitive film without reinforcement), photosensitive film reinforced with the reinforcement of Example 2 (photosensitive film reinforced with acid gelatin), and photosensitive film reinforced with the reinforcement of Comparative Example 1 (photosensitive film reinforced with alkaline gelatin).

[0096] The experimental procedure was as follows: The three types of photosensitive films were cut into samples weighing 1.00 ± 0.01 g each. Each sample was added to 100 mL of ultrapure water and slowly stirred in a water bath at 38 ± 1 °C for 24 hours. After filtration, a small amount of the solution was taken, and its pH was measured using an S210 pH meter. After multiple pH measurements, the test results are as follows: Figure 1 As shown.

[0097] See Figure 1 It can be seen that the pH of undeveloped photosensitive films is mostly stable at 6.5, the pH of photosensitive films developed and strengthened with acidic gelatin is mostly stable at 6.2, and the pH of photosensitive films developed and strengthened with alkaline gelatin is mostly stable at 6.5. This means that the pH of photosensitive films developed and strengthened with alkaline gelatin remains consistent with the original film and does not change the film's acidity or alkalinity. This is because the main component of the photosensitive film in dry-plate glass film is gelatin, which exists in a gel state in a 10%–15% solution, exhibiting overall gel properties. The viscosity and strength of the gel are strongly affected by pH, temperature, and electrolytes. If the pH of the system decreases, the surface tension of the gelatin gel will also decrease linearly, macroscopically manifesting as physical expansion and contraction of the photosensitive film. Due to the difference in expansion and contraction rates between the photosensitive film and the glass dry plate, as the surface tension of the photosensitive film further decreases, the entire glass film will exhibit a series of serious defects such as cracking, warping, or detachment, resulting in severe loss of image information.

[0098] 2. Gelatin viscosity analysis

[0099] Test samples: Developmental reinforcements obtained in Example 2 and Comparative Example 1

[0100] Test Procedure: Pour the aforementioned developing agent into a Type 4 viscosity cup. Block the outlet of the cup with your finger until the liquid surface protrudes above the upper edge of the cup. If air bubbles are present, wait for them to rise to the surface. Then, use a clean, flat glass plate to scrape away excess liquid and air bubbles along the edge, ensuring the liquid level is level with the upper edge of the flow cup. Release your finger and start a stopwatch. The liquid will flow out in a continuous line. Stop the stopwatch when the line begins to break. Record the stopwatch reading t. (For accuracy, multiple measurements can be taken for comparison.) The sample temperature during the test is 25±1℃. Calculate the kinematic viscosity V using the following formula:

[0101] When t < 23 s, V = (t - 11) / 0.154

[0102] When 23s ≤ t < 150s, V = (t - 6.0) / 0.223

[0103] Where: t - outflow time, s; V - kinematic viscosity, mm 2 / S.

[0104] Viscosity statistics as follows Figure 2 As shown. (a) shows the viscosity results of the developing binder for acid-processed gelatin; (b) shows the viscosity results of the developing binder for alkali-processed gelatin.

[0105] See Figure 2 The developing and strengthening agent corresponding to the acid-processed gelatin in Comparative Example 1 had an average viscosity of 122.23 mm. 2 / S; Example 2: Development and strengthening agent corresponding to alkali gelatin, with an average viscosity of 177.65 mm. 2 It is evident that the viscosity of the developing and reinforcing agent formed from alkali-processed gelatin is greater than that formed from acid-processed gelatin. Gelatin, a natural collagen, consists of three left-handed helical peptide chains intertwined to form a right-handed superhelical structure. Over time, cross-linking occurs between these collagen chains. During gelatin extraction, these cross-links are not completely destroyed, ultimately existing as β-chains, γ-chains, and even higher molecular weight components. The increased content of these components leads to a higher viscosity of the gelatin. The high viscosity of the developing and reinforcing agent formed from alkali-processed gelatin indicates a higher content of high molecular weight components such as β-chains and γ-chains in its microstructure. These high molecular weight components are beneficial for enhancing the adhesion of the reinforcing agent when reinforcing glass substrates, helping it to better fill and repair scratches and small pores on the surface of damaged substrates. Therefore, choosing alkali-processed gelatin as the raw material for the developing and reinforcing agent can achieve better protective effects.

[0106] Experiment 2, Zeta potential test

[0107] The compatibility between solutes and the stability of the solvent are compared by testing the zeta potential.

[0108] Since gelatin-based strengthening agents are classified as colloids, the zeta potential, also known as the electrokinetic potential or zeta charge, is the potential at the shear plane and is an important indicator of the stability of colloidal dispersions. The significance of the zeta potential lies in its correlation with the stability of the colloidal dispersion.

[0109] Test samples: Developmental reinforcements of Example 2 and Comparative Example 2

[0110] Test procedure: The two samples were diluted with ultrapure water to a mixed solution with a mass concentration of 0.2%. 1.3 ml of the mixed solution was pipetted into sample vials, and the potential was measured using an S2107857 laser particle size zeta potential meter. The test results are as follows: Figure 3 As shown, (a) is the potential-time curve; (b) is the potential value result.

[0111] See Figure 3 It can be seen that the Zeta potential of the development and strengthening agent with Kathon added is -36.33 mV, while that without Kathon is -25.14 mV. Since the Zeta potential is a measure of the strength of the repulsive or attractive forces between particles, the smaller the molecules or dispersed particles, the higher the absolute value (positive or negative) of the Zeta potential, and the more stable the system, meaning that dissolution or dispersion can resist aggregation. Conversely, the lower the Zeta potential (positive or negative), the more inclined it is to condense or aggregate, meaning that the attractive force exceeds the repulsive force, and the dispersion is disrupted, resulting in condensation or aggregation. Therefore, it shows that the addition of Kathon greatly improves the dispersion performance of the solute in the development and strengthening agent, making the development and strengthening agent system more stable.

[0112] Experiment 3, X-ray diffraction analysis

[0113] Test samples: Development and strengthening agents from Examples 1 to 3

[0114] Test Procedure: Four dry glass slides were prepared according to the method in Example 4. One was a blank sample, i.e., without the development and strengthening agent. The remaining three dry glass slides were coated with the development and strengthening agents of Examples 1 to 3, respectively, according to the method in Example 4. Then, X-ray diffraction tests were performed on the dry glass slides with a step angle of 0.01°, a voltage of 40kV, a current of 30mA, and a scanning range of 2θ = 5° to 50°. The X-ray diffraction spectra of the uncoated and coated samples with different mass concentrations of alkaline gelatin development and strengthening agents are shown below. Figure 4 As shown, (a) is the peak area of ​​the triple helix characteristic peak; (b) is the X-ray diffraction pattern.

[0115] See Figure 4Both uncoated and coated dry-plate glass films exhibit diffraction peaks at 2θ = 8° and 2θ = 44°. Since imaging on a dry-plate glass film involves the reduction of silver halide to elemental silver, the photosensitive film on the film will show characteristic X-ray diffraction peaks of silver at 2θ = 44°, with no significant difference in peak position or width. Therefore, it can be seen that coating with different concentrations of alkaline gelatin as a developing agent does not significantly alter the phase and crystal structure of elemental silver on the surface of the dry-plate glass film.

[0116] Further from Figure 4 It was observed that at the characteristic peak at 2θ = 8°, several sets of peaks showed some differences. This is because gelatin is a water-soluble semi-crystalline biopolymer derived from animal collagen. At 2θ = 8°, its triple-helix structure exhibits X-ray diffraction characteristic peaks. The amount of triple-helix structure directly determines the degree of physical cross-linking of gelatin and affects its subsequent thermal, mechanical, and chemical properties. Therefore, through Origin peak analysis, the peak areas of the four sets of triple-helix characteristic peaks were calculated as follows: without the development and strengthening agent, the peak area of ​​the triple-helix characteristic peak on the dry glass film was 61.36; with the development and strengthening agent of Example 1, the peak area of ​​the triple-helix characteristic peak on the dry glass film was 74.35; with the development and strengthening agent of Example 2, the peak area of ​​the triple-helix characteristic peak on the dry glass film was 96.01; and with the development and strengthening agent of Example 3, the peak area of ​​the triple-helix characteristic peak on the dry glass film was 91.76. The peak area of ​​the triple helix characteristic peaks shows that when the mass concentration of alkaline gelatin in the developing agent is 6% (6% refers to the mass concentration of alkaline gelatin in the mixed solution), the content of the gelatin triple helix structure in the photosensitive film on the dry plate glass film can be increased to the maximum extent. This improves and optimizes the physical and chemical properties of the dry plate glass film from the source, thereby preventing and protecting against defects in the dry plate glass film.

[0117] Experiment 4, Stability Analysis

[0118] Test samples: Development and strengthening agents from Examples 1 to 3

[0119] Test Procedure: Four dry glass plates were prepared according to the method in Example 4. One plate was a blank sample, i.e., without the development and hardening agent. The remaining three dry glass plates were coated with the development and hardening agents of Examples 1 to 3, respectively, according to the method in Example 4. Then, the photosensitive film on each dry glass plate was peeled off, and the thermal stability of the photosensitive film was determined using a STA449F5 thermal analyzer. Because the photosensitive film preparation process contains S and N elements, the heating rate was set to 100℃ / min, the carrier was nitrogen, and the temperature range was 20–600℃. The TG curves were obtained as follows. Figure 5 As shown; where: (a) is the test result without the development reinforcement agent; (b) is the test result with the development reinforcement agent of Example 1; (c) is the test result with the development reinforcement agent of Example 2; (d) is the test result with the development reinforcement agent of Example 3; in (a) to (d), the left figure is the trend of temperature and mass fraction; the right figure is the trend of temperature and heat flow.

[0120] See Figure 5 The TG curves of the four types of photosensitive films mentioned above were initially relatively stable, and the DTG curves did not show a sharp drop. This is because the moisture in the photosensitive film evaporates before decomposition, resulting in a certain weight loss. Whether the photosensitive film is uncoated or coated with a developer, it is essentially an animal glue. When animal glue is heated, it first undergoes a state change, transitioning from a glassy or hard state to a rubbery or soft state. The temperature at which this change occurs is called the glass transition temperature (Tg), a crucial parameter affecting the mechanical and adhesive properties of animal glue. The DSC curves show that the Tg of the uncoated photosensitive film with the developer and hardener is 228°C; the Tg of the photosensitive film coated with the developer and hardener of Example 1 is 249.5°C; the Tg of the photosensitive film coated with the developer and hardener of Example 2 is 331°C; and the Tg of the photosensitive film coated with the developer and hardener of Example 3 is 336°C. From the above, it can be seen that when the content of alkaline gelatin is 6% and 9% (6% and 9% refer to the mass concentration of alkaline gelatin in the mixed solution, respectively), the glass transition temperature Tg of the photosensitive film can be increased.

[0121] See Figure 5 The temperature after the glass transition temperature Tg is the denaturation temperature Td of animal glue, and the peak area of ​​the endothermic peak corresponding to the denaturation temperature Td is the deformation enthalpy ΔH of animal glue. d Denaturation temperature Td, denaturation enthalpy ΔH d This is closely related to the transformation of the multihelical structure of polypeptide chains within animal glue to an amorphous state. The ΔH of the uncoated photosensitive film with development and reinforcement agents... d The concentration was 0.6 J / g; the ΔH of the development and reinforcement photosensitive film of Example 1 was coated. d The concentration was 2.548 J / g; the ΔH of the development and reinforcement photosensitive film of Example 2 was also measured. d The concentration was 6.372 J / g; the ΔH of the development and reinforcement photosensitive film of Example 3 was also measured. d The result is 4.385 J / g. As can be seen from the above results, when the development and strengthening agent of Example 2 is applied, the denaturation temperature of the photosensitive film can be effectively increased, so that the photosensitive film can retain the multi-helical structure in the animal glue to the greatest extent before the denaturation temperature. This corresponds to the X-ray diffraction results and corroborates each other.

[0122] In summary, applying the development and strengthening agent of this invention to a dry plate glass substrate can improve the heat resistance of the photosensitive film on the dry plate glass substrate.

[0123] Experiment 5: Microscopic Morphology Analysis

[0124] Test samples: Development and strengthening agents from Examples 1 to 3

[0125] Test Procedure: Four dry glass slides were prepared according to the method in Example 4. One was a blank sample, i.e., without development and hardening agent coating. The remaining three dry glass slides were coated with development and hardening agents from Examples 1 to 3, respectively, according to the method in Example 4. Then, the dry glass slides coated with different mass concentrations of alkaline gelatin development and hardening agents, as well as the dry glass slides without development and hardening agent coating, were cut to appropriate sizes using a glass cutter. The cut dry glass slides were then fixed on the scanning stage with conductive adhesive. After gold sputtering for 120 seconds, the surface morphology of the dry glass slides was observed using an SU3500 tungsten filament scanning electron microscope. The results are as follows: Figure 6 As shown, a represents the morphology of the uncoated reinforcement; b represents the morphology of the reinforcement in Example 1; c represents the morphology of the reinforcement in Example 2; d represents the morphology of the reinforcement in Example 3; subscript 1 indicates magnification of 500x, and subscript 2 indicates magnification of 1000x.

[0126] See Figure 6The morphology images, from a1 and a2, show that without the development and strengthening agent, the surface of the photosensitive film on the dry plate glass film is rough and has small pores. This is because the main component of the photosensitive film is gelatin. Under the influence of changes in environmental temperature and humidity, the content of the triple helix structure of gelatin polypeptide chains decreases, the colloid loses its adhesion, and the long chains of gelatin are attached with trace amounts of macromolecular substances. Under natural conditions, large particles are prone to shrinkage and aggregation, which leads to wrinkling and lifting of the film surface and damages the image information of the film. From b1 and b2, it can be observed that after development and strengthening with the development and strengthening agent of Example 1, the pores on the surface of the photosensitive film on the dry plate glass film have been partially filled. However, due to the low concentration of alkaline gelatin, its molecular weight is insufficient to encapsulate the gelatin in the photosensitive film, and the development and strengthening agent cannot form a uniform and dense protective layer. As observed in c1 and c2, after development and reinforcement with the developing and reinforcing agent of Example 2, the molecules on the surface of the photosensitive film on the dry plate glass film are uniformly dispersed, and the particle size is basically the same. This indicates that after development and reinforcement with this agent, the gelatin macromolecules in the photosensitive film on the dry plate glass film no longer adsorb to each other, forming a dense protective layer and achieving the expected protective effect. As observed in d1 and d2, after development and reinforcement with the developing and reinforcing agent of Example 3, although there is no phenomenon of macromolecules adsorbing to each other on the photosensitive film on the dry plate glass film, the excessively high concentration of alkaline gelatin affects the leveling properties of the developing and reinforcing agent. The molecular distribution density on the surface of the photosensitive film on the dry plate glass film is uneven, and molecules accumulate in some areas, which reduces the visibility of the photosensitive image on the dry plate glass film. Therefore, the developing and reinforcing agent of Example 2 (the mass concentration of alkaline gelatin in the mixed solution is 6%) has the best protective effect on the photosensitive film on the dry plate glass film.

[0127] Experiment 6: Transmittance and Reflectance Test

[0128] Test samples: Development and strengthening agents from Examples 1 to 3

[0129] Test Procedure: Four dry glass plates were prepared according to the method in Example 4. One plate was a blank sample, i.e., without the development and strengthening agent. The remaining three dry glass plates were coated with the development and strengthening agents of Examples 1 to 3, respectively, according to the method in Example 4. Then, the transmittance and reflectance of the dry glass plates coated with different development and strengthening agents and those without development and strengthening agents were tested using a UV-Lambda950 ultraviolet-near-infrared spectrophotometer at a wavelength range of 500-800 nm and a scan rate of 300 nm / min. The test results are as follows: Figure 7 As shown, (a) represents the reflectance result; (b) represents the transmittance result.

[0130] See Figure 7As can be seen from (a), in the visible light range, the reflectance of the photosensitive film on the dry plate glass film is 20% when no developing agent is applied, and the reflectance of the photosensitive film on the dry plate glass film is between 12% and 17% when the developing agent of Examples 1 to 3 is applied. This indicates that the reflectance of the photosensitive film on the dry plate glass film is significantly reduced after developing and strengthening with the developing agent. The reflectance is 12% after applying the developing agent of Example 2 (the mass concentration of alkaline gelatin in the mixed solution is 6%), which is the most significant reduction in reflectance.

[0131] See Figure 7 As can be seen from (b), in the visible light range, the transmittance of the photosensitive film on the dry plate glass film is 64% when no developing agent is applied, and the transmittance of the photosensitive film on the dry plate glass film is between 65% and 68% when the developing agent of Examples 1 to 3 is applied. This indicates that the transmittance of the photosensitive film on the dry plate glass film is significantly improved after developing and strengthening with the developing agent. Moreover, the transmittance is 68% after applying the developing agent of Example 2 (the mass concentration of alkaline gelatin in the mixed solution is 6%), which shows the most significant improvement in transmittance.

[0132] In summary, the reinforcing agent with added alkaline gelatin has a smoothing and repairing effect on the film substrate, reducing its surface roughness and decreasing light reflection and scattering on the film surface, resulting in an 8% reduction in film reflectivity; it also increases the light transmittance of the photosensitive film, increasing the film transmittance by 4%. As a macromolecular substance, alkaline gelatin, after being coated on the surface of the photosensitive film, can fill the gaps caused by scratches. A smooth and flat photosensitive film not only facilitates the interpretation of the image information inherent in the film itself but also eliminates some light reflection, thereby preventing the specular effect from affecting the film's imaging quality. However, excessive alkaline gelatin molecules can aggregate, which in turn affects the smoothness of the film, reducing its transmittance and increasing its reflectivity. Verification showed that the reinforcing agent of Example 2 had the best improvement effect on the photosensitive film.

[0133] Experiment 7. Degradation Performance Analysis

[0134] The wrinkling, cracking, and warping that occur on dry-plate glass films during prolonged storage are due to the transformation of the gelatin multi-helix structure in the photosensitive film, leading to varying degrees of degradation. Gelatin degradation is essentially a process of breaking and hydrolyzing peptide bonds in its polypeptide chains. This peptide bond breakage and hydrolysis produces acidic substances, thus lowering the pH of the entire system. Therefore, this experiment utilizes this characteristic to conduct in vitro degradation tests on the photosensitive films before and after coating with a developing and hardening agent.

[0135] Test samples: Development and strengthening agents from Examples 1 to 3

[0136] Test Procedure: Four dry glass plates were prepared according to the method in Example 4. One plate was a blank sample, i.e., no developing agent was applied. The remaining three dry glass plates were coated with the developing agents from Examples 1 to 3, respectively, according to the method in Example 4. The photosensitive film was then peeled off from each dry glass plate and cut into samples weighing approximately 2g. The samples were placed in phosphate buffered saline (PBS) and placed in a water bath shaker at 37.6°C with a rotation speed of 30 r / min. The solution was removed every five days, and the pH was measured using an S210 pH meter. The degree of degradation of the photosensitive film was determined based on the pH value. The results are as follows: Figure 8 As shown.

[0137] See Figure 8 Initially, the pH of each photosensitive film sample remained stable at around 7.6. After the in vitro degradation test began, the pH of the buffer solution of all four photosensitive films decreased until the curve flattened on day 16, indicating that the pH of each system began to stabilize. Without the development and hardening agent, the pH of the buffer solution of the photosensitive film decreased by 16% on day 16; after applying the development and hardening agent of Example 1, the pH of the buffer solution of the photosensitive film decreased by 13% on day 16; after applying the development and hardening agent of Example 2, the pH of the buffer solution of the photosensitive film decreased by 11% on day 16; and after applying the development and hardening agent of Example 3, the pH of the buffer solution of the photosensitive film decreased by 12% on day 16. Therefore, it can be clearly seen that after coating with the development and strengthening agent provided by the present invention, the degradation rate of the gelatin in the photosensitive film can be effectively slowed down; when the development and strengthening agent of Example 2 (the mass concentration of alkaline gelatin in the mixed solution is 6%) is coated, the pH value of the buffer solution of the photosensitive film decreases the least, indicating that the degradation rate of the gelatin in the photosensitive film is the slowest.

[0138] Experiment 8: Photosensitive film adhesion test

[0139] This experiment was conducted according to GB / T 1720-2020 "Coating Film Cross-Cross Test", using an electric adhesion tester to test the adhesion. Figure 9 The adhesion is rated as shown.

[0140] Test samples: Development reinforcements from Examples 1 to 3.

[0141] Test Procedure: Four dry glass substrates were prepared according to the method in Example 4. One was a blank sample, i.e., without the development and strengthening agent. The remaining three dry glass substrates were coated with the development and strengthening agents of Examples 1 to 3, respectively, according to the method in Example 4. Then, each dry glass substrate was subjected to wet heat aging for 9 days. After aging, the substrates were removed. They were then placed at room temperature (temperature 25±3℃, relative humidity 30%~50%) for 72 hours for testing. During the test, a 100g weight was added, and the substrates were drawn clockwise at a uniform speed of 80r / min. The test was stopped when the scratch length reached 7.5±0.5cm. The substrates were then removed, and the adhesion of the developed and strengthening agent was rated. The adhesion test results are as follows: Figure 10 As shown in Table 2, the adhesion test results are as follows.

[0142] Table 2 Adhesion test of photosensitive film on glass film after damp heat aging.

[0143] Film-forming materials Surface drying time Film color Adhesion rating Uncoated hardener --- --- Level 7 Example 1 40s transparent Level 5 Example 2 50s transparent Level 2 Example 3 55s Transparent and slightly yellow Level 3

[0144] From Table 2 and Figure 10 It can be seen that without any reinforcement treatment, the photosensitive film on the dry plate glass film is very easy to peel off after being subjected to high temperature and high humidity conditions. After treatment with the developing and reinforcing agent of Example 1, the film formation speed is fast, the film is transparent after formation, and it does not affect the imaging effect of the film, but the adhesion is poor and the film is easy to peel off. After treatment with the developing and reinforcing agent of Example 2, the film is transparent after formation, the film formation speed is relatively fast, and the adhesion is good. After treatment with the developing and reinforcing agent of Example 3, the adhesion is good, but the film formation speed is slow, and there is a slight yellowing after formation, which will cause a color difference between the dry plate glass film before and after reinforcement. Therefore, after treatment with the developing and reinforcing agent of Example 2 (the mass concentration of alkaline gelatin in the mixed solution is 6%), a protective film with good adhesion and transparency can be quickly formed on the dry plate glass film, which improves the mechanical strength of the surface of the dry plate glass film and prevents it from being damaged and peeling off during later storage, thus achieving the purpose of reinforcing and protecting the dry plate glass film.

[0145] Experiment 9: Performance Testing of Reinforcing Agent Films

[0146] The purpose of this experiment is to test the properties of the development-reinforced film formed after development reinforcement by the development reinforcement agent.

[0147] Test samples: Development reinforcements from Examples 1 to 3.

[0148] Test Procedure: Three glass slides were taken, and the developing and hardening agents of Examples 1 to 3 were coated on them respectively. During the test, the developing and hardening agent was coated evenly on the surface of the glass slide, then the slide was placed horizontally on a flat table and left to stand for 72 hours to form a thin film of developing and hardening agent on the surface of the slide. Haze and contact angle tests were then performed on the developing and hardening agent films on the surfaces of the three glass slides.

[0149] 1. Haze test

[0150] Test principle: Haze refers to the percentage of transmitted light intensity that deviates from the incident light by more than 2.5° to the total transmitted light intensity. The more light is scattered, the higher the haze value, the more blurred the image, and the less conducive it is to film protection.

[0151] Test Method: Refer to the method in GB / T 2410-2008 "Determination of Light Transmittance and Haze of Transparent Plastics". Specifically, the glass slides forming the developing hardener film were equilibrated for 40 hours at a temperature of 23±3℃ and a relative humidity of 40%~60%. After equilibration, five different points were selected on each slide, and the haze was measured using a TH-110 haze meter under the conditions of a D65 light source, a measuring aperture of 7mm, and a wavelength range of 400~700nm. After the test, the glass slides were placed in an HCP damp heat aging chamber with a temperature of 50℃ and a relative humidity of 80% for 9 days. Every 3 days, the glass slides were removed from the chamber, and the haze was measured according to the above method. The test results are as follows. Figure 11 As shown; where: the left side is a statistical chart of haze changes; the right side, from top to bottom, shows the error bars after treatment with the reinforcing agent in Examples 1, 2 and 3.

[0152] from Figure 11It can be seen that, without aging treatment, the haze of the development hardener film treated with the development hardener in Example 3 is significantly higher than that of the other examples. This indicates that the development hardener film treated with the development hardener in Example 3 has more light scattering, which has a greater impact on image clarity. The development hardener films treated with the development hardener in Examples 1 and 2 show little difference in haze without aging treatment. However, after damp heat aging, the haze of the development hardener film treated with the development hardener in Example 1 fluctuates significantly. This indicates that degradation may have occurred in the damp heat environment, leading to increased haze and reduced film clarity. Furthermore, the haze test was conducted using [specific parameters not specified in the original text]. Five points on the film surface were tested. The haze test values ​​of the developing agent film after treatment with the developing agent in Example 1 showed a large difference, which can be clearly seen from the size of the error bar on the right side of the figure. This indicates that the developing agent film of Example 1 is not uniform, which is consistent with the aforementioned morphology test results. On the other hand, the developing agent film after treatment with the developing agent in Example 2 had a lower haze and did not change significantly before and after damp heat aging. It can be seen that this developing agent, when reinforcing dry plate glass film, not only does not affect the clarity of the image on the dry plate glass film, but also has good anti-aging properties, avoiding the risk of damage to the image information of the dry plate glass film due to long-term storage.

[0153] 2. Contact Angle Test

[0154] Test principle: The smaller the contact angle, the better the hydrophilicity of the sample surface; conversely, the larger the contact angle, the better the hydrophobicity of the sample surface.

[0155] Test Method: Using a KRUSS-DSA100 optical contact angle meter, the contact angles of the development and hardening agent films formed on the surfaces of three glass slides after coating with the development and hardening agent were measured at a droplet volume of 2 μL. After the test, the glass slides were placed in an HCP damp heat aging chamber, with the temperature set at 50℃ and the relative humidity at 80% for 9 days. Every 3 days, the glass slides were removed from the chamber, and their contact angles were measured according to the above procedure. The test results are as follows. Figure 12 As shown.

[0156] from Figure 12The contact angles of the development and strengthening agent films with different mass concentrations before and after hygrothermal aging treatment show that: as the hygrothermal aging time increases, the contact angles of all three development and strengthening agent films gradually decrease, but the contact angle of the development and strengthening agent film corresponding to Example 2 is always larger than that of the development and strengthening agent films corresponding to other examples; when the contact angle is smaller and the hydrophilicity is better, the development and strengthening agent film is more susceptible to moisture and damage in a humid environment; conversely, when the contact angle is larger and the hydrophobicity is better, the development and strengthening agent film can better protect the dry plate glass substrate and prevent moisture and pollutants in the environment from damaging the dry plate glass substrate. Therefore, the development and strengthening agent of Example 2 (the mass concentration of alkaline gelatin in the mixed solution is 6%) can provide better reinforcement and protection for the dry plate glass substrate.

[0157] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A developing agent characterized by comprising: The alkali gelatin, kathon, water-based epoxy resin and water are prepared by mass ratio of 3-9:0.1-0.3:0.1-0.6:91-97.

2. The developing agent according to claim 1, characterized by The alkali gelatin, kathon, water-based epoxy resin and water are prepared by mass ratio of 3-9:0.1-0.3:0.1-0.6:91-97.

3. The developing agent according to claim 1, wherein The Zeta potential of the appearance reinforcing agent is -36.33 mV, which is measured by diluting the appearance reinforcing agent to a mixed solution with a mass concentration of 0.2% using ultrapure water.

4. The method for preparing the enhancement agent as described in claim 1, characterized in that, The preparation method comprises the following steps: S1, according to the amount of alkali gelatin, kathon, water-based epoxy resin and water are prepared; S2, the alkali gelatin is dissolved in water and heated to 45-55 DEG C, and stirred uniformly to obtain a mixed solution; S3, kathon and water-based epoxy resin are added to the mixed solution of step S2 in sequence, and mixed uniformly to complete the preparation.

5. The application of the appearance reinforcing agent in preventing the disease of dry plate glass negative.

6. Use according to claim 5, characterized in that, The application is: the appearance reinforcing agent is uniformly coated on the surface of the dry plate glass negative, and the dry plate glass negative is placed horizontally for 48-72 hours, the appearance of the dry plate glass negative is reinforced, and the prevention of the disease of the dry plate glass negative is completed.

7. Use according to claim 6, characterized in that, The appearance reinforcing agent can reduce the degradation rate of gelatin on the dry plate glass negative.

8. Use according to claim 6, characterized in that, The appearance reinforcing agent can improve the mechanical strength and light transmittance of the surface of the dry plate glass negative, and reduce the reflectivity of the surface of the dry plate glass negative.

9. Use according to claim 6, characterized in that, The disease of the dry plate glass negative is cracking, warping, peeling and / or powdering; the dry plate glass negative after coating the appearance reinforcing agent appears diffraction peaks at 2θ=8° and 2θ=44°.

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