Application of softening and toughening agent in treatment of early dry plate glass negative disease

Abstract

The application belongs to the technical field of film repair and treatment, and relates to application of a softening toughening agent in treatment of early dry plate glass film diseases, and the softening toughening agent comprises a surfactant, ethanol and water, and the mass ratio of the surfactant, the ethanol and the water is 0.5-1.1:130-135:30-35; the softening toughening agent further comprises water-based epoxy resin B63, and the mass of the water-based epoxy resin B63 is 0.5-1.2 times the mass of the surfactant. The softening toughening agent is formed by using the surfactant, the ethanol and the water, can ensure that the surface of the adhesive film is smoother and more even, has small swelling deformation, is beneficial to re-sticking repair, and can be well used in treatment of dry plate glass film diseases.

Description

Technical Field

[0001] This invention belongs to the field of film repair technology, and relates to the application of a softening and toughening agent in treating early-stage dry-plate glass film defects. Background Technology

[0002] Dry plate glass negatives (also known as glass negatives) originated in the mid-19th century. For over a century, people have used glass negatives to photograph a vast number of authentic historical scenes and figures, creating unique and precious photographic archives. Glass negatives are a very valuable and special form of archival material with significant collectible value. However, during long-term storage, due to internal factors and external storage environments, glass negatives may exhibit defects such as wrinkling, cracking, peeling, and even detachment of the emulsion layer. This is because the gelatin in the emulsion layer is a product of collagen denaturation, belonging to the category of protein macromolecules. It possesses properties similar to protein macromolecules, but the unique structure of gelatin molecules determines its unique physicochemical properties. Gelatin molecular chains are formed by peptide bonds between the carboxyl and amino groups of amino acids. These peptide bonds undergo hydrolysis under the influence of water molecules, thus causing the glass... During storage, glass negatives are susceptible to hydrolysis due to high temperature and humidity. Alternating temperature and humidity changes cause the gelatin in the emulsion layer to repeatedly expand and contract, leading to cracking, peeling, and detachment of the emulsion layer during long-term storage. Ultimately, this results in the formation of large agglomerates on the photosensitive film of the emulsion layer, making the surface of the photosensitive film rough. These defects in the photosensitive film of the emulsion layer not only significantly reduce the artistic, research, and historical value of the glass negative, but also cause the chemical bonds of the gelatin inside the emulsion layer to break, damaging the molecular structure and ultimately causing the glass negative to be completely destroyed.

[0003] Therefore, it is necessary to repair and protect the aforementioned defects in glass negatives. Currently, there are almost no reports on specialized repair methods for glass negatives, both domestically and internationally. Based on literature review, the following flattening methods can be used as a reference for paper artifacts exhibiting wrinkles and creases: high-temperature softening, air pressure flattening, boiling, and mechanical flattening.

[0004] The high-temperature softening method involves placing the wrinkled, cracked, or warped glass film in a muffle furnace and treating it with a low-temperature, high-temperature process. The temperature is set below 200°C, exceeding the thermal softening point of the emulsion layer photosensitive film on the dry glass film, thus altering its physical properties. However, when flattening the emulsion layer photosensitive film using this method, excessively high temperatures can cause the peptide bonds formed by the carboxyl and amino groups of the gelatin molecules in the film to break. This can lead to thermal degradation or particle aggregation of the emulsion layer photosensitive film, causing it to adhere and become impossible to separate, posing a greater challenge to subsequent re-attachment and repair.

[0005] The boiling method involves placing wrinkled, cracked, or warped glass slides in deionized water and allowing them to smooth out at a specific temperature. However, this method is suitable for substances that are stable to both moisture and heat. The gelatin molecules in the emulsion layer of the photosensitive film are hydrophilic and dissolve when heated. The boiling method causes the peptide bonds in the gelatin to hydrolyze under the influence of water molecules. This macroscopically manifests as a direct breakage of the emulsion layer of the photosensitive film, which is detrimental to the smoothing and repair of the film's emulsion layer.

[0006] Furthermore, when repairing cracked, warped, or detached glass sheets, the emulsion layer material on the glass sheet is silver bromide emulsion with a paste-like gelatin as its main component. Since gelatin is non-degradable, it is only soluble in pure water. Water is needed to swell the wrinkled emulsion layer so that the wrinkled areas can be flattened. However, it is also necessary to avoid excessive water absorption during softening, which can easily cause swelling and deformation. Aligning the seams during repair is not conducive to re-attaching the glass.

[0007] The above flattening methods for repairing simulated samples cannot effectively flatten the emulsion layer of the glass film, and some methods may even cause greater damage to the photosensitive film of the emulsion layer. Summary of the Invention

[0008] To address the limitations of existing methods in effectively flattening the emulsion layer of glass film and hindering its repositioning and repair, this invention provides an application of a softening and toughening agent in treating early-stage dry-plate glass film defects.

[0009] This invention uses surfactants, ethanol, water, and a very small amount of waterborne epoxy resin to form a softening and toughening agent, which can ensure that the surface of the emulsion layer photosensitive film is smoother and flatter, with less swelling and deformation, which is conducive to re-attachment and repair, and can be well used in the treatment of defects in dry plate glass film.

[0010] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A softening and toughening agent comprising a surfactant, ethanol, and water, wherein the mass ratio of the surfactant, ethanol, and water is 0.5~1.1:130~135:30~35; and the surfactant is TO-8 or OP-10.

[0011] Further specified, the mass ratio of the surfactant, ethanol and water is 1:134:33.

[0012] Furthermore, the ethanol is anhydrous ethanol.

[0013] Furthermore, the softening and toughening agent also includes waterborne epoxy resin B63, wherein the mass of waterborne epoxy resin B63 is 0.5 to 1.2 times the mass of the surfactant.

[0014] Furthermore, the mass of the waterborne epoxy resin B63 is one time the mass of the surfactant.

[0015] The application of the softening and toughening agent described above in the treatment of early-stage dry plate glass film defects.

[0016] Further specifying, the early defects of dry plate glass film are wrinkling, cracking, or warping.

[0017] Further specifying, the steps for using the softening and toughening agent to treat early-stage dry-plate glass film defects include: 1) Spray the softening and toughening agent onto the surface of the early dry plate glass substrate to be treated, and spread the softening and toughening agent evenly to wet the early dry plate glass substrate; 2) Cover the surface of the early dry plate glass film with polytetrafluoroethylene (PTFE) coated cloth and press it with a heavy object, and let it stand for 72 hours. 3) Remove the heavy objects and PTFE coated cloth, and flatten the surface of the early dry glass substrate to complete the treatment of the disease.

[0018] The beneficial effects of this invention are: 1. This invention uses surfactants, ethanol, and water to form a softening and toughening agent. The surfactants used include ether groups, which do not dissociate in aqueous solution and exhibit excellent wetting properties. Furthermore, the neutral molecules in these surfactants have high surface activity, good solubilizing properties, and minimal irritation. This maximizes the surface activity of the sample system without damaging the photosensitive film of the glass film emulsion. Since the surfactants do not exist in an ionic state in solution, they are highly stable, not easily affected by strong electrolytes, and resistant to acids and alkalis. They also have good compatibility with anhydrous ethanol. Therefore, when this softening and toughening agent is applied to the surface of wrinkled, cracked, or warped glass films, it does not cause strong adsorption, ensuring a smoother and flatter surface of the photosensitive film emulsion with minimal swelling and deformation, facilitating re-attachment and repair. It is well-suited for repairing dry-plate glass films. Furthermore, the addition of water-based epoxy resin B63 synergistically enhances the smoothing and repair effect with the surfactants and ethanol.

[0019] 2. The softening and toughening agent of the present invention has appropriate hydrophilicity, which can fully and effectively wet the hardened and brittle emulsion layer on the photosensitive film without excessive swelling, thus affecting the subsequent re-attachment and repair. Attached Figure Description

[0020] Figure 1 SEM image of the photosensitive emulsion layer on a glass film; Figure 2 Infrared spectrum of the photosensitive emulsion layer on a glass film; Figure 3The surface contact angle of the photosensitive emulsion film in the glass film emulsion layer; Figure 4 The softness of the photosensitive emulsion film in the glass film emulsion layer; Figure 5 A 2D morphology image of the photosensitive emulsion layer on a glass film; Figure 6 A 3D morphology image of the photosensitive emulsion layer on a glass film. Figure 7 Statistical graph of surface roughness before and after coating of photosensitive emulsion film on glass film with reagent; Figure 8 The color difference value of the reagent used to coat the photosensitive emulsion layer of the glass film after damp heat aging. Detailed Implementation

[0021] The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0022] The softening and toughening agent provided by this invention comprises a surfactant, ethanol, and water. The mass ratio of the surfactant, ethanol, and water is 0.5~1.1:130~135:30~35.

[0023] In this invention, the surfactant is either TO-8 or OP-10. TO-8 is a nonionic surfactant, referring to isotridecyl alcohol ether; OP-10, whose full name is sodium n-octylhexyloxy polyethylene glycol ether sulfate, is a compound with surfactant properties. Its chemical formula is C8H2O. 17 C6H 40 (C2H 40 )nSO3Na, where n represents the number of repetitions of the ethoxy group.

[0024] In this invention, the mass ratio of surfactant, ethanol and water is 1:134:33, 1:132.53:33, and 1:130:33.

[0025] Preferably, the mass ratio of surfactant, ethanol and water is 1:134:33.

[0026] Preferably, the surfactant is TO-8. The ethanol is anhydrous ethanol.

[0027] Furthermore, the softening and toughening agent provided by the present invention also includes waterborne epoxy resin B63, wherein the mass of waterborne epoxy resin B63 is 0.5 to 1.2 times the mass of the surfactant. For example, the mass of waterborne epoxy resin B63 is 0.5, 0.6, 0.8, 0.9, 1.0, 1.1, and 1.2 times the mass of the surfactant.

[0028] Preferably, the mass of waterborne epoxy resin B63 is 1 times the mass of the surfactant.

[0029] The application of the softening and toughening agent provided by this invention in treating early-stage dry-plate glass film defects.

[0030] Specifically, early defects in dry-plate glass film include wrinkling, cracking, or warping.

[0031] In this invention, the steps for using a softening and toughening agent to treat early-stage dry-plate glass film defects include: 1) Spray the softening and toughening agent onto the surface of the early dry plate glass substrate to be treated, and spread the softening and toughening agent evenly to wet the early dry plate glass substrate; 2) Cover the surface of the early dry plate glass film with polytetrafluoroethylene (PTFE) coated cloth and press it with a heavy object, and let it stand for 72 hours. 3) Remove the heavy objects and PTFE coated cloth, and flatten the surface of the early dry glass substrate to complete the treatment of the disease.

[0032] The following examples verify the performance of the softening and toughening agent provided by the present invention in repairing dry plate glass film, but these examples should not be construed as limiting the scope of protection of the present invention.

[0033] The materials and instruments used in the following embodiments are as follows.

[0034] 1. Materials Gelatin, anhydrous ethanol, Shanghai Maclean Biochemical Technology 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.; isomeric tridecyl alcohol polyoxyethylene ether 8 (TO-8), Shandong Yousuo Chemical Technology Co., Ltd.

[0035] 2. Instruments HX3002T electronic balance, Cixi Tiandong Weighing Instrument Factory; WP-UP-WF-40 micro-analytical ultrapure water system, Sichuan Woteer Water Treatment Equipment Co., Ltd.; 85-2 digital display constant temperature magnetic stirrer, Hangzhou Instrument & Motor Co., Ltd.; FQ-KTD300 adjustable distance paper cutter, Sichuan Changjiang Paper Instrument Co., Ltd.; electric heating blower dryer, Beijing Kewei Yongxing Instrument Co., Ltd.; laser confocal scanning microscope, Keyence Corporation, Japan; tungsten filament scanning electron microscope, Hitachi High Technology Corporation; video optical contact angle tester, KRUSS, Germany; DCP-RRY1000 softness tester, Sichuan Changjiang Paper Instrument Co., Ltd.; colorimeter, X-Rite Instruments, USA; Fourier transform infrared spectrometer, Platinum Elmer, USA.

[0036] Example 1 The softening and toughening agent provided in this embodiment comprises a surfactant, ethanol, and water, with a mass ratio of surfactant, ethanol, and water of 0.6 g: 79.52 g: 19.88 g (1: 132.53: 33). The surfactant is TO-8.

[0037] In this embodiment, the surfactant is TO-8, the ethanol is anhydrous ethanol, and the water is ultrapure water.

[0038] Specifically, take 0.6g of surfactant TO-8 and 79.52g of anhydrous ethanol, add them to 19.88g of ultrapure water, and mix them evenly to obtain a softening and toughening agent.

[0039] Example 2 The softening and toughening agent provided in this embodiment includes a surfactant, ethanol, waterborne epoxy resin B63 and water, with the mass ratio of surfactant, ethanol and water being 0.6g:79.52g:19.88g; and the mass ratio of surfactant to waterborne epoxy resin B63 being 1:1.

[0040] In this embodiment, the surfactant is TO-8, the ethanol is anhydrous ethanol, and the water is ultrapure water.

[0041] Specifically, take 0.6g of surfactant TO-8, 79.52g of anhydrous ethanol, and 0.6g of waterborne epoxy resin B63 using a dropper. Add all three to 19.88g of ultrapure water and mix thoroughly to obtain a softening and toughening agent.

[0042] Example 3 The softening and toughening agent provided in this embodiment includes a surfactant, ethanol, waterborne epoxy resin B63, and water; the mass ratio of surfactant, ethanol, and water is 0.8:132.53:33; and the mass ratio of surfactant to waterborne epoxy resin B63 is 1:1.

[0043] Example 4 The softening and toughening agent provided in this embodiment includes a surfactant, ethanol, waterborne epoxy resin B63, and water; the mass ratio of surfactant, ethanol, and water is 0.9:132.53:33; and the mass ratio of surfactant to waterborne epoxy resin B63 is 1:1.

[0044] Example 5 The softening and toughening agent provided in this embodiment includes a surfactant, ethanol, waterborne epoxy resin B63, and water; the mass ratio of surfactant, ethanol, and water is 1.1:132.53:33; and the mass ratio of surfactant to waterborne epoxy resin B63 is 1:1.

[0045] Comparative Example 1 The softening and toughening agent provided in this comparative example is obtained by mixing 0.6g of surfactant TO-8 and 99.4g of ultrapure water.

[0046] The softening and toughening agents used in the above examples and comparative examples were used to soften, toughen, and flatten the wrinkled emulsion layer mold, thereby comparing and evaluating the performance of the softening and toughening agents.

[0047] I. Preparation of wrinkled emulsion-layer photosensitive film samples According to the book "Photographic Chemistry," the preparation method for dry glass plate negatives was found. The general steps are as follows: 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 halides are removed. Reheat the emulsion; the photographic emulsion preparation is now complete. Apply the emulsion evenly to a smooth, warm steel plate or glass slide within 25 hours. After drying, an unexposed glass negative is obtained. Place the unexposed glass negative in a perforated black box, find a suitable exposure time, and take a simple photograph. Finally, develop, stop developing, fix, and wash the photographed negative; the simulated sample preparation is complete. Place the negative in a dry heat aging chamber for more than 72 hours, then place it in an aging chamber with a certain temperature and humidity for 72 hours. Finally, place it in a desiccator filled with pure water overnight and air dry to obtain a wrinkled emulsion-layer photosensitive film (also known as photosensitive film or emulsion-layer photosensitive film) sample.

[0048] II. Softening, Toughening, and Flattening Process The softening and toughening agents of Comparative Example 1, Example 1, and Example 2 are respectively labeled as Solvent No. 1, Solvent No. 2, and Solvent No. 3.

[0049] The wrinkled emulsion layer photosensitive mold sample was softened, toughened, and flattened using three solvents, and the specific steps are as follows.

[0050] (1) Place the wrinkled emulsion photosensitive film sample on a clean copy table, and use an ultra-fine spray bottle to evenly spray the above three softening and toughening agents onto the surface of the wrinkled emulsion photosensitive film sample. Use a fine brush to gently spread the softening and toughening agents evenly on the sample surface so that the softening and toughening agents completely wet the sample.

[0051] (2) After the surface is flattened, cover the surface of the sample with polytetrafluoroethylene (PTFE) varnish cloth, press the PTFE varnish cloth with a heavy object, and let it stand for 72 hours.

[0052] (3) Finally, the weight and polytetrafluoroethylene coated cloth were removed, and the wrinkled emulsion photosensitive film sample was flattened.

[0053] III. Characterization Tests and Results 1. Microscopic morphology (SEM) analysis The three softening and toughening agents were coated onto the surface of the prepared emulsion film. After drying at room temperature, conductive adhesive was used to fix the emulsion film without softening and toughening agents and the emulsion films coated with the three softening and toughening agents onto the stage. Then, gold was sputtered to make it conductive and eliminate charge accumulation. The microstructure of the samples was observed at 1000x magnification under vacuum conditions. The test results are as follows. Figure 1 As shown.

[0054] from Figure 1 It can be seen that the surface of the untreated aged photosensitive film is significantly rough, with obvious large particle agglomeration. This is because after long-term aging, the gelatin in the glass film emulsion layer undergoes significant shrinkage and embrittlement, resulting in large-sized spherulite structures. The SEM image of the aged photosensitive film treated with reagent one shows a relatively smooth surface, but some large particles are still present. This is because TO-8, as a nonionic surfactant, reduces the surface tension of the photosensitive film, thus reducing the overall size of the gelatin film's spherulite structure. The SEM image of the simulated photosensitive film treated with reagent two shows... There are no obvious large particle agglomerates on the surface. This is because the ethanol molecule contains hydroxyl groups, which can form hydrogen bonds with the hydroxyl groups on the gelatin film molecules. This interaction force disperses the large-sized spherulite structure of the gelatin film. The SEM image of the aged photosensitive film treated with reagent No. 3 shows that, compared with the first two groups of reagents, the surface of the emulsion layer treated with this reagent is smoother and flatter, and there are no particle agglomerates at all. The addition of water-based epoxy resin B63 further disperses and eliminates the spherulite structure of the gelatin. Macroscopically, the hardened and brittle emulsion layer is fully and effectively wetted and flattened, which is very beneficial for subsequent re-attachment and repair.

[0055] 2. Fourier Transmission Infrared Spectroscopy (FT-IR) Analysis The wavelength range of 450–4000 cm⁻¹ was measured using a PE-Frontier Fourier transform infrared spectrometer. -1 Under the specified conditions, infrared spectroscopy tests were performed on emulsion films without softening and toughening agents and emulsion films coated with the three softening and toughening agents respectively. The test results are as follows: Figure 2 As shown.

[0056] Figure 2 Infrared spectra of the untreated glass film with a wrinkled emulsion layer and the film treated with three different softening and toughening agents are shown. The main component of the emulsion layer photosensitive film is gelatin. The characteristic peaks of the gelatin film are those of amide A, amide B, amide I, amide II, and amide III, with corresponding wavenumbers at 3285, 3075, 1680, 1540, and 1240 cm⁻¹, respectively. -1 Nearby. According to Figure 2 Wavenumber 1700 cm can be observed -1 Distinct characteristic peaks appeared on both sides, representing the carbonyl stretching vibration peaks of gelatin amide I. The carbonyl stretching vibration peaks of the emulsion film treated with the softening and toughening agent were much smoother and less intense than those of the untreated emulsion film, indicating that all three softening and toughening agents effectively reduced the crystallinity of the gelatin film emulsion. The infrared spectrum and SEM images corroborated each other, demonstrating that the softening and toughening agents effectively eliminated the spherulitic structure of the gelatin film emulsion, making it easier to flatten during the softening process and facilitating subsequent repair. A comparison of four groups at 1700 cm⁻¹... -1 The carbonyl stretching vibration peaks show that the peaks after incorporating waterborne epoxy resin B63 (reagent number two) are the smoothest and have the lowest intensity, but the peak positions have not changed. This indicates that the addition of waterborne epoxy resin B63 has a strong intermolecular interaction with the gelatin film of the emulsion layer, but it does not cause a qualitative change in the chemical properties of the gelatin film of the emulsion layer.

[0057] 3. Contact Angle Test During the contact angle test, the softening and toughening agents from Examples 3 to 5 were used to flatten three wrinkled emulsion-layer photosensitive film samples. Comparative Example 1 used reagent No. 1, Example 1 used reagent No. 2, Example 2 used reagent No. 3 (C), Example 3 used reagent No. 3 (A), Example 4 used reagent No. 3 (B), and Example 5 used reagent No. 3 (D).

[0058] Three points were taken at different locations on the emulsion film without the softening and toughening agent, and on the emulsion films coated with the softening and toughening agents of Examples 1-5 and the comparative examples, respectively. Contact angle tests were performed using ultrapure water, and the average values ​​were taken. Each film sample was then subjected to a one-minute follow-up test to observe its hydrophilicity and hydrophobicity, thereby further determining the wettability of the softening and toughening agent on the sample. The test results are as follows: Figure 3 As shown.

[0059] Figure 3 The results show the contact angle test results for untreated aged photosensitive films and aged photosensitive films treated with six different softening and toughening agents.

[0060] from Figure 3It can be seen that the contact angles of all tested films were less than 90°, indicating that both the aged photosensitive film and the film before and after treatment were hydrophilic. Specifically, the contact angle of the aged photosensitive film treated with reagent No. 1 was 78°, which was smaller and more hydrophilic than the untreated film. This could easily lead to excessive water absorption, swelling, and deformation of the glass film emulsion layer during subsequent re-attachment and repair, hindering alignment of the seams during repair. In contrast, the contact angles of the aged photosensitive films treated with reagents No. 2 (Example 1) and No. 3 (Examples 2-5) were larger than those of the untreated films. This is because, at the microscopic level, the hydroxyl groups of ethanol can form hydrogen bonds with the hydroxyl groups of gelatin, and the hydroxyl groups of aqueous epoxy can form hydrogen bonds with the amino groups of gelatin. The intermolecular force of hydrogen bonding between hydroxyl and amino groups is greater than that between hydroxyl groups themselves. Therefore, selecting reagents No. 2 and No. 3 as softening and toughening agents can slightly improve the hydrophobicity of the glass film emulsion layer, preventing excessive swelling and deformation in the reagents, while also avoiding excessive hydrophobicity that could hinder subsequent re-attachment and repair.

[0061] By changing the mass of the surfactant in reagent No. 3, it can be seen that as the amount of surfactant increases, its surface hydrophobicity increases slightly. When the mass percentage ratio of surfactant: ethanol: water is 1:134:33, its contact angle is 88°. When the mass percentage of surfactant is further increased, its contact angle is around 90°. Although the hydrophobicity is further improved compared to the unsoftened aged photosensitive film, its wetting effect is not good enough, which is not conducive to subsequent re-application.

[0062] 4. Softness test According to GB / T 8942—2002, a hand-feel softness tester was used to test the softness of emulsion films without softening and toughening agents and emulsion films coated with three different softening and toughening agents. The test results are as follows: Figure 4 As shown in Table 1.

[0063] Softness refers to the vector sum of the bending resistance of a specimen of a certain width and length and the frictional force between the specimen and the slit when the specimen is pressed into a slit to a certain depth using a plate-shaped probe under conditions specified by the standard. The smaller this value, the softer the specimen is.

[0064] Figure 4The results of the softness tests on untreated simulated aged photosensitive emulsion films and those treated with three different softening and toughening protective agents show that the photosensitive emulsion film treated with reagent No. 1 has the highest softness value, at 12.66 mN. The softness of the photosensitive emulsion films treated with reagents No. 2 and No. 3 is also significantly improved, reaching 340.33 mN and 331.33 mN, respectively. Experimental verification also shows that excessively soft photosensitive emulsion films tend to stick together during later restoration, making them difficult to flatten and re-attach. The photosensitive emulsion films treated with reagents No. 2 and No. 3 have a suitable level of softness, which facilitates flattening, prevents sticking, and allows for better adhesion to the glass during subsequent re-attachment. This reduces the possibility of air bubbles forming between the emulsion layer and the glass supporting the film, thus benefiting the long-term preservation of the restored glass film.

[0065] Table 1. Softness of the photosensitive film in the emulsion layer of glass film 5. Surface 2D and 3D morphology and roughness testing The 2D and 3D morphologies of the emulsion films without softening and toughening agents, and those coated with three different softening and toughening agents, were observed and their roughness was measured using a Keyence VK-X250K laser confocal scanning microscope. The test results were corrected using Keyence multi-file analysis software to obtain the roughness parameters Sa, Sz, Str, Spc, and Sdr. The test results are shown below. Figure 5 , Figure 6 and Figure 7 As shown.

[0066] Figure 5 The images, in order, show the 2D morphology of the wrinkled gelatin film on glass slides after 72 hours of dry heat aging: uncoated, coated with reagent 1, coated with reagent 2, and coated with reagent 3. It can be seen that the surface of the aged emulsion film without any reagent coating is uneven. The surfaces of the emulsion films coated with reagent 1 and reagent 2 do not have significant undulations, but there are some large and small bumps and depressions. The surface of the emulsion film coated with reagent 3 is relatively smooth, with only a few dot-like bumps. This indicates that the incorporation of waterborne epoxy resin B63 can effectively restore the smoothness of the aged wrinkled gelatin film, and it did not wrinkle again after 72 hours in the dry heat aging chamber, demonstrating its durability.

[0067] Figure 6 The images, in order, show the 3D morphology of the wrinkled emulsion film on glass slides after 72 hours of dry heat aging, with the films coated with reagent No. 1, reagent No. 2, and reagent No. 3, respectively. This is combined with... Figure 7The surface roughness parameter chart clearly shows that all three softening and toughening agents effectively reduce the surface roughness of the wrinkled emulsion film. Sa represents the arithmetic mean height, a height parameter of the surface properties. The wrinkled emulsion film without softening and toughening agent coating has the highest arithmetic mean height, while the wrinkled emulsion film coated with reagent No. 3 has the lowest arithmetic mean height. This indicates that reagents No. 2 and No. 3 significantly reduce the wrinkling degree of the emulsion film, making it smoother. Sz represents the maximum height, the height difference between the highest and lowest points on the surface. The wrinkled emulsion film without softening and toughening agent coating has either large protrusions or deep depressions, while the emulsion film coated with softening and toughening agent is relatively smooth. The surface roughness chart also clearly shows that Sz is much smaller after adding waterborne epoxy resin B63 compared to the previous three, indicating that the surface protrusions and depressions are effectively improved. Str is the aspect ratio of the surface properties. A value close to 0 indicates the presence of striations in the sampling area D, while a value close to 1 indicates that D is direction-independent. Spc is the arithmetic mean curvature of the peaks. A smaller value indicates a more rounded point of contact with other objects, while a larger value indicates a sharper point of contact. The softening and toughening agent Spc, after coating with waterborne epoxy resin B63, effectively reduces this curvature, indicating that the incorporation of waterborne epoxy resin B63 smooths out the originally wrinkled, sharp protrusions of the emulsion film. Sdr is the interfacial expansion area ratio. When the surface is completely flat, the value of Sdr is 0, while from... Figure 7 It can be seen that the Sdr of the wrinkled emulsion film coated with water-based epoxy resin B63 softening and toughening agent is close to 0, which indicates that the surface of the emulsion layer is already very flat at this time.

[0068] 6. Optical performance (color difference value) test Color difference testing is essential in the field of cultural heritage restoration, as it is crucial to minimize aesthetic alterations caused by the preservation and treatment of artifacts during the restoration process. The X-RiteVS-450 colorimeter was used to test the color difference of emulsion films without softening and toughening agents at different aging times, as well as emulsion films coated with three different softening and toughening agents. The test results are as follows: Figure 8 As shown in Table 2.

[0069] Figure 8 The following are the color difference values ​​of the wrinkled emulsion layer photosensitive film of glass slides after different humid heat aging times: uncoated, coated with reagent No. 1, coated with reagent No. 2, and coated with reagent No. 3. Figure 8It can be seen that the color difference values ​​of the untreated photosensitive film after 3, 6, 9, and 12 days of humid heat aging were 2.2, 2.4, 2.52, and 2.6, respectively, showing a gradual increase in color difference. While the color difference values ​​of the photosensitive film treated with the softening and toughening agent changed after humid heat aging, the changes were relatively small. Table 2 shows that the photosensitive film coated with reagent No. 2 had the smallest color difference value. This is because TO-8 in reagent No. 1 is milky white, and its application to the sample surface slightly alters the sample's color. After TO-8 is fully mixed and reacted with anhydrous ethanol, reagent No. 2 becomes a colorless and transparent liquid. The water-based epoxy resin B63 added to reagent No. 3 is slightly yellowish, and its application to the sample surface causes a slight color change, but the color difference values ​​are all within 3, having virtually no impact on the original appearance of the photosensitive film. Figure 8 It can be seen that the color difference curve of the photosensitive film coated with reagent No. 3 after wet heat aging has the smallest change range and the curve tends to be stable, which means that it also effectively protects the photosensitive film.

[0070] Table 2. Statistics on color difference of reagents used for coating the emulsion layer and photosensitive film on glass film after damp heat aging. Unprocessed Treatment of Reagent No. 1 Treatment with Reagent No. 2 After treatment with reagent No. 3 Non-moist heat aging 0 2.3 1.7 2.31 Moist heat aging 3 days 2.2 2.68 1.9 2.35 Moist heat aging 6 days 2.4 2.71 1.98 2.37 9 days of damp heat aging 2.52 2.71 2.11 2.4 Moist heat aging 12 days 2.6 2.75 2.12 2.51 In summary, the softening and toughening agent provided by this invention has a good effect on treating early-stage defects in dry-plate glass substrates. The treated film surface is smoother and flatter, with less swelling and deformation, which is conducive to re-attachment and repair. It can be well used in the repair of dry-plate glass substrates.

[0071] The above description, in conjunction with specific preferred embodiments, provides a further detailed explanation of the present invention. It should not be construed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, various simple deductions or substitutions can be made without departing from the concept of the present invention, and all such modifications and substitutions should be considered within the scope of protection of the present invention.

Claims

1. A softening and toughening agent, characterized in that, The softening and toughening agent is composed of a surfactant, ethanol and water, wherein the mass ratio of the surfactant, ethanol and water is (0.5~1.1):(130~135):(30~35); the surfactant is TO-8 and the ethanol is anhydrous ethanol.

2. The softening and toughening agent according to claim 1, characterized in that, The mass ratio of the surfactant, ethanol and water is 1:134:

33.

3. A softening and toughening agent, characterized in that, The softening and toughening agent is composed of a surfactant, ethanol, water and waterborne epoxy resin B63, wherein the mass ratio of the surfactant, ethanol and water is (0.5~1.1):(130~135):(30~35); the mass of the waterborne epoxy resin B63 is 0.5~1.2 times the mass of the surfactant, the surfactant is TO-8 and the ethanol is anhydrous ethanol.

4. The softening and toughening agent according to claim 3, characterized in that, The mass of the waterborne epoxy resin B63 is 1 times the mass of the surfactant.

5. The application of a softening and toughening agent as described in claim 1 or 3 in the treatment of early-stage dry-plate glass film defects.

6. The application according to claim 5, characterized in that, The early defects of dry plate glass film are wrinkling, cracking, or peeling.

7. The application according to claim 6, characterized in that, The steps for using the softening and toughening agent to treat early-stage dry-plate glass film defects include: 1) Spray the softening and toughening agent onto the surface of the early dry plate glass substrate to be treated, and spread the softening and toughening agent evenly to wet the early dry plate glass substrate; 2) Cover the surface of the early dry plate glass film with polytetrafluoroethylene (PTFE) coated cloth and press it with a heavy object, and let it stand for 72 hours. 3) Remove the heavy objects and PTFE coated cloth, and flatten the surface of the early dry glass substrate to complete the treatment of the disease.

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