An industrial x-ray film and a method of manufacturing the same

Abstract

The application provides an industrial X-ray film and a preparation method thereof, and relates to the field of industrial X-ray films. The preparation method of the industrial X-ray film comprises the following steps: preparing halogenated silver cubic particle emulsion, in-situ composite modification, preparing emulsion layer coating liquid, and coating and forming. The preparation method of the industrial X-ray film can effectively overcome the problems of obvious image granularity, silver atom transverse migration and merging of developing centers between adjacent particles, improve the image resolution, improve the utilization rate of X-ray photons, effectively improve the photosensitive sensitivity and photosensitive response range, and improve the long-term stability of the industrial X-ray film, in particular, the pressure stability and the environmental stability.

Description

Technical Field

[0001] This invention relates to the field of industrial X-ray film, and in particular to an industrial X-ray film and its preparation method. Background Technology

[0002] In the field of industrial flaw detection, the main methods currently used include radiographic testing, ultrasonic testing, magnetic particle testing, eddy current testing, and penetrant testing. Radiographic testing is the most frequently used method in industrial flaw detection. Its main mechanism is to utilize the penetrating power of radiation to detect internal or surface defects in workpieces or welds, especially the internal structure of welded components and steel plates. Industrial flaw detection films are often used in combination with metal foil (intensifying screens) and radiation. Silver halide particles absorb the energy generated by the radiation irradiating the workpiece, exposing the photosensitive material. After development, a black silver image is formed, which is used to detect minute defects on the workpiece.

[0003] Industrial non-destructive testing (NDT) uses X-rays or gamma rays as its light source. X-rays can be generated by X-ray machines or high-energy X-ray accelerators, while gamma rays can be generated by radioactive isotopes. X-rays and gamma rays are light of specific wavelengths, each with strong penetrating power; the shorter the wavelength, the stronger the penetrating power.

[0004] In the preparation of industrial flaw detection films, emulsions are usually synthesized using methods such as double injection and neutral emulsification. Among them, the crystal form of silver halide particles in the emulsion of X-ray film can be cubic particles, potato-shaped particles, and T-particles, with an average particle size of 0.2-0.6μm. The emulsion particles are monodisperse and have high resolution, which helps to improve the contrast of the film.

[0005] However, existing industrial X-ray films exhibit noticeable graininess in their images during application, exhibiting issues such as lateral migration of silver atoms and merging of development centers between adjacent particles, thus requiring further optimization of image resolution. Furthermore, existing industrial X-ray films cannot achieve efficient utilization of X-ray photons, have a high critical exposure, and require further optimization of photosensitivity and photosensitivity response range.

[0006] Furthermore, existing industrial X-ray films have poor pressure and environmental stability. They are prone to generating fog after being placed and stored in high temperature and high humidity or high pressure environments, and their long-term stability needs to be further improved.

[0007] Based on this, an industrial X-ray film and its preparation method are provided, which can effectively overcome the problems of obvious image graininess, lateral migration of silver atoms and merging of development centers between adjacent particles. While improving image resolution, it can also improve the utilization rate of X-ray photons, effectively improve photosensitivity and photosensitivity response range, and improve the long-term stability of industrial X-ray film, especially pressure stability and environmental stability. This has important technical significance and research value. Summary of the Invention

[0008] To address the technical problems existing in the prior art, this invention provides a method for preparing industrial X-ray film, which effectively overcomes the issues of significant image graininess, lateral migration of silver atoms, and merging of development centers between adjacent particles. While improving image resolution, it also enhances the utilization rate of X-ray photons, effectively improving photosensitivity and photosensitivity response range; and improves the long-term stability of industrial X-ray film, particularly its pressure stability and environmental stability. This invention also provides industrial X-ray film prepared using the aforementioned method.

[0009] To solve the above technical problems, the technical solution adopted by the present invention is as follows: A method for preparing industrial X-ray film includes the following steps: preparing silver halide cubic particle emulsion, in-situ composite modification, preparing emulsion coating liquid, and coating and molding. The method for preparing silver halide cubic particle emulsion is as follows: photographic gelatin, polyvinylpyrrolidone, and sodium dioctyl succinate sulfonate are added to deionized water, mixed evenly, and the pH is adjusted to 5.5 and pAg to 7.43; silver nitrate solution and potassium bromide solution are added dropwise at a temperature of 55-60℃; after the addition is complete, the mixture is kept warm and stirred to obtain silver halide cubic particle emulsion. The in-situ composite modification method is as follows: under a temperature of 55-60℃, the pH of the silver halide cubic particle emulsion is adjusted to neutral, and zinc nitrate aqueous solution and 2-methylimidazole aqueous solution are added dropwise in sequence; after the addition is completed, the mixture is kept at 32-35℃ and stirred to obtain a reaction solution; the reaction solution is subjected to ultrafiltration treatment until it is reduced to 64-67% of its original volume to obtain the modified emulsion of in-situ composite ZIF-8. After the modified emulsion is used to prepare the emulsion coating liquid, it is coated and molded to obtain industrial X-ray film.

[0010] Preferably, in the preparation of the silver halide cubic particle emulsion, the weight ratio of deionized water, photographic gelatin, polyvinylpyrrolidone, and sodium dioctyl succinate sulfonate is 950:50-52:4.5-4.8:0.2-0.25. The total volume ratio of deionized water to the added silver nitrate solution is 1:1.1-1.2; The total volume ratio of deionized water to the added potassium bromide solution is 1:1.1-1.2.

[0011] Preferably, in the preparation of the silver halide cubic particle emulsion, the molecular weight of polyvinylpyrrolidone is 45,000-55,000; The concentration of silver nitrate solution is 2.9-3.1 mol / L, and the concentration of potassium bromide solution is 2.95-3.15 mol / L.

[0012] Furthermore, in the preparation of the silver halide cubic particle emulsion, under a temperature of 55-60℃, the dropping rate of the silver nitrate solution and the potassium bromide solution is first controlled to be constant at 4-4.5 mL / min for the first addition. After the first addition is completed, the mixture is kept at the temperature and stirred. Then, the initial dropping rate of the silver nitrate solution and the potassium bromide solution is controlled to be 2-2.2 mL / min, the acceleration of the dropping rate is 1.2-1.3 mL / min, and the final dropping rate is 30-32 mL / min for the second addition. After the second addition is completed, the mixture is kept at the temperature and stirred to obtain the silver halide cubic particle emulsion.

[0013] Preferably, the first addition time is 5-6 minutes, and the heat preservation and stirring time after the first addition is 15-20 minutes; The second addition should be done in 50-55 minutes, and the subsequent warming and stirring time should be 15-25 minutes.

[0014] Preferably, in the in-situ composite modification, the dropping rate of the zinc nitrate aqueous solution is 1.5-2 mL / min; The dropping rate of 2-methylimidazole aqueous solution is 0.7-1 mL / min; After the addition is complete, maintain the temperature at 32-35℃ and stir for 3-4 hours. The molecular weight cutoff for ultrafiltration is 50-60 kDa.

[0015] Preferably, in the in-situ composite modification, the concentration of the zinc nitrate aqueous solution is 0.1-0.12 mol / L; The concentration of 2-methylimidazole aqueous solution is 0.3-0.36 mol / L; The volume ratio of silver halide cubic particle emulsion, zinc nitrate hexahydrate aqueous solution, and 2-methylimidazole aqueous solution is 100:23-25:23-25.

[0016] Furthermore, the method for preparing the emulsion coating solution is as follows: at a temperature of 45-50°C, alkylphenol polyoxyethylene ether, carboxymethyl cellulose, and neutral silica sol are added to the modified emulsion, mixed evenly, and then photographic gelatin is added to adjust the viscosity to 12-18 mPa·s to obtain the emulsion coating solution. The weight ratio of the in-situ composite modified emulsion, alkylphenol polyoxyethylene ether, carboxymethyl cellulose, and neutral silica sol is 1000:6-6.5:4-4.3:8-8.5.

[0017] Furthermore, the coating method involves using a micro-gravure coating process to coat the emulsion coating liquid onto both sides of the substrate, controlling the single-sided coating thickness of the emulsion coating liquid to be 8-10 μm; then, an isolation layer coating liquid and a protective layer coating liquid are sequentially coated on the outer surface of the emulsion layer to obtain an industrial X-ray film. The isolation layer coating liquid includes alkylphenol polyoxyethylene ether, glutaraldehyde, deionized water, and gelatin; The protective coating liquid includes alkylphenol polyoxyethylene ether, silicone oil, glutaraldehyde, deionized water, and gelatin.

[0018] An industrial X-ray film is prepared using the aforementioned method.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) In the preparation method of industrial X-ray film of the present invention, in the step of preparing silver halide cubic particle emulsion, polyvinylpyrrolidone, sodium dioctyl succinate sulfonate and double injection process are used. Through the steric hindrance and electrostatic stabilization effect of the composite stabilizing system composed of polyvinylpyrrolidone and sodium dioctyl succinate on the particle preparation material, the uniform nucleation and controllable growth of silver halide cubic particles are effectively achieved, and silver halide cubic particles with uniform size are prepared, thereby reducing image graininess and improving image resolution. Simultaneously, in the in-situ composite modification step, zinc nitrate aqueous solution and 2-methylimidazole aqueous solution are sequentially added to the silver halide cubic particle emulsion. Through in-situ composite, a metal-organic framework (ZIF-8) is further composited onto the silver halide cubic particles. The ZIF-8 isolates each silver halide cubic particle, inhibiting the lateral migration of silver atoms and the merging of development centers between adjacent particles during development. This improves the image edge blurring caused by silver diffusion, enhances image edge sharpness, further improves the image resolution and photosensitivity of industrial X-ray film, broadens its dynamic range, and enhances its long-term stability. The aforementioned techniques work synergistically to effectively overcome the problems of significant image graininess, lateral silver atom migration, and merging of development centers between adjacent particles. While improving image resolution, it also increases the utilization rate of X-ray photons, effectively improving photosensitivity and photosensitivity response range; and enhances the long-term stability of industrial X-ray film, especially its pressure stability and environmental stability.

[0020] (2) Upon testing, the equivalent circular diameter of the silver halide cubic particles obtained in the preparation of the industrial X-ray film of the present invention is 0.26-0.30 μm, and the coefficient of variation of size is 7.1-7.6%; the background fog density D0 of the obtained industrial X-ray film is 0.03-0.04, and the modulation transfer function MTF is... 50 The sensitivity is 93-96 lp / mm, the average slope G is 3.7-3.8, the relative sensitivity S is 205-210, the exposure latitude L is 3.5-3.6, and the maximum density D is... max The specific sensitivity is 5.5-5.6, the contrast coefficient γ is 4.3-4.5, and the specific sensitivity S R The scratch resistance is 229-233%, and the scratch resistance is 1.20-1.23N.

[0021] (3) The industrial X-ray film of the present invention, after being stored in a constant temperature and humidity environment of 55°C and 85% for 28 days, has a background fog density increase ΔD0 of only 0.03; when subjected to an application of 50 N / cm 2 Under pressure conditions, after maintaining the pressure for 6 hours, the increase in the background fog density ΔD0 of the film was only 0.02.

[0022] (4) The preparation method of the industrial X-ray film of the present invention is simple, easy to control, and conducive to large-scale industrial production. Detailed Implementation

[0023] To provide a clearer understanding of the technical features, objectives, and effects of this invention, specific embodiments are now described. It should be noted that the following detailed descriptions are exemplary and intended to provide further explanation of the invention. Unless otherwise specified, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0024] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the exemplary embodiments of the present invention. As used herein, "first," "second," etc., are used to distinguish similar objects and are not used to describe a particular order or sequence. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0025] This invention provides a method for preparing industrial X-ray film, comprising the following steps: preparing a silver halide cubic particle emulsion, in-situ composite modification, preparing an emulsion coating solution, and coating and forming. The method for preparing silver halide cubic particle emulsion is as follows: photographic gelatin, polyvinylpyrrolidone, and sodium dioctyl succinate sulfonate are added to deionized water, mixed evenly, and the pH is adjusted to 5.5 and pAg to 7.43; silver nitrate solution and potassium bromide solution are added dropwise at a temperature of 55-60℃; after the addition is complete, the mixture is kept warm and stirred to obtain silver halide cubic particle emulsion. The in-situ composite modification method is as follows: under a temperature of 55-60℃, the pH of the silver halide cubic particle emulsion is adjusted to neutral, and zinc nitrate aqueous solution and 2-methylimidazole aqueous solution are added dropwise with stirring in sequence; after the addition is completed, the mixture is kept at 32-35℃ with stirring to obtain a reaction solution; the reaction solution is subjected to ultrafiltration treatment to 64-67% of the original volume to obtain the modified emulsion of in-situ composite ZIF-8; After the modified emulsion is used to prepare the emulsion coating liquid, it is coated and molded to obtain industrial X-ray film.

[0026] In the preparation of industrial X-ray film of this invention, in the step of preparing silver halide cubic particle emulsion, polyvinylpyrrolidone, sodium dioctyl succinate sulfonate, and a double-injection process are used. The composite stabilizing system composed of polyvinylpyrrolidone and sodium dioctyl succinate exerts steric hindrance and electrostatic stabilization on the particle preparation material, effectively achieving uniform nucleation and controllable growth of silver halide cubic particles. This results in uniformly sized silver halide cubic particles, reducing image graininess and improving image resolution. Simultaneously, in the in-situ composite modification step, zinc nitrate aqueous solution and 2-methylimidazole aqueous solution are added sequentially to the silver halide cubic particle emulsion. Through in-situ composite, a metal-organic framework (ZIF-8) is further composited onto the silver halide cubic particles. The isolation effect of ZIF-8 on each silver halide cubic particle inhibits the lateral migration of silver atoms and the merging of development centers between adjacent particles during development, improving the image edge blurring problem caused by silver diffusion, increasing image edge sharpness, and further improving the image resolution of industrial X-ray film.

[0027] Furthermore, when silver halide cubic particles are combined with metal-organic frameworks (ZIF-8), ZIF-8 can pre-absorb and enrich X-ray photons before transferring them to the silver halide cubic particles during subsequent exposure processes, effectively improving the utilization rate of X-ray photons and achieving enhanced sensitivity. At the same time, the porous structure of ZIF-8 can also absorb and enrich secondary electrons generated during exposure, increasing the probability of collisions with the silver halide cubic particles, further reducing the critical exposure rate required to form a stable latent image, and effectively improving the photosensitivity of industrial X-ray film.

[0028] Furthermore, when silver halide cubic particles are combined with metal-organic framework ZIF-8, weak signals can be effectively captured in low-exposure areas due to the sensitizing effect of ZIF-8; in high-exposure areas, the confinement effect of ZIF-8 effectively prevents excessive merging and saturation of developing silver; and effectively prevents chemical crosstalk between low-exposure and high-exposure areas, thus broadening the dynamic range of industrial X-ray film.

[0029] Furthermore, after the silver halide cubic particles are combined with the metal-organic framework ZIF-8, the barrier effect of ZIF-8 on the silver halide cubic particles effectively isolates them from contact with harmful substances such as water vapor and oxygen in the external environment; and improves the compressive strength of the silver halide cubic particles, thereby improving the long-term stability of industrial X-ray film, especially its pressure stability and environmental stability.

[0030] In a preferred embodiment of the present invention, the weight ratio of deionized water, photographic gelatin, polyvinylpyrrolidone, and sodium dioctyl succinate sulfonate in the preparation of the silver halide cubic particle emulsion is 950:50-52:4.5-4.8:0.2-0.25. The total volume ratio of deionized water to the added silver nitrate solution is 1:1.1-1.2; The total volume ratio of deionized water to the added potassium bromide solution is 1:1.1-1.2.

[0031] In a preferred embodiment of the present invention, the molecular weight of polyvinylpyrrolidone in the preparation of the silver halide cubic particle emulsion is 45,000-55,000. The concentration of silver nitrate solution is 2.9-3.1 mol / L, and the concentration of potassium bromide solution is 2.95-3.15 mol / L.

[0032] In a further embodiment of the present invention, in the preparation of the silver halide cubic particle emulsion, under a temperature of 55-60°C, the dropping rate of the silver nitrate solution and the potassium bromide solution is first controlled to be constant at 4-4.5 mL / min for the first dropping. After the first dropping is completed, the mixture is kept warm and stirred. Then, the initial dropping rate of the silver nitrate solution and the potassium bromide solution is controlled to be 2-2.2 mL / min, the acceleration of the dropping rate is 1.2-1.3 mL / min, and the final dropping rate is 30-32 mL / min for the second dropping. After the second dropping is completed, the mixture is kept warm and stirred to obtain the silver halide cubic particle emulsion.

[0033] In this embodiment of the invention, preferably, the first droplet addition time is 5-6 minutes, and the heat preservation and stirring time after the first droplet addition is 15-20 minutes; The second addition should be done in 50-55 minutes, and the subsequent warming and stirring time should be 15-25 minutes.

[0034] In the preparation of silver halide cubic particle emulsion in this embodiment of the invention, by controlling the precursor concentration, raw material ratio, and dropwise addition process during the preparation of silver halide cubic particles, the uniform nucleation and controllable growth process of silver halide cubic particles is further optimized, the crystal defects of silver halide cubic particles are reduced, which is conducive to the preparation of silver halide cubic particles with uniform size, and further improves the photosensitivity and pressure stability of the prepared industrial X-ray film.

[0035] In this embodiment of the invention, preferably, in the in-situ composite modification, the dropping rate of the zinc nitrate aqueous solution is 1.5-2 mL / min; The dropping rate of 2-methylimidazole aqueous solution is 0.7-1 mL / min; After the addition is complete, maintain the temperature at 32-35℃ and stir for 3-4 hours. The molecular weight cutoff for ultrafiltration is 50-60 kDa.

[0036] In this embodiment of the invention, preferably, the concentration of the zinc nitrate aqueous solution in the in-situ composite modification is 0.1-0.12 mol / L; The concentration of 2-methylimidazole aqueous solution is 0.3-0.36 mol / L; The volume ratio of silver halide cubic particle emulsion, zinc nitrate hexahydrate aqueous solution, and 2-methylimidazole aqueous solution is 100:23-25:23-25.

[0037] In the in-situ composite modification step of this invention, by selectively choosing process parameters such as the specifications, raw material ratio, dropping rate, and reaction time of zinc nitrate aqueous solution and 2-methylimidazole aqueous solution, the uniform composite of silver halide cubic particles and metal-organic framework ZIF-8 is further optimized.

[0038] In this embodiment of the invention, the method for preparing the emulsion coating liquid is as follows: at a temperature of 45-50°C, alkylphenol polyoxyethylene ether, carboxymethyl cellulose, and neutral silica sol are added to the modified emulsion, mixed evenly, and then photographic gelatin is added to adjust the viscosity to 12-18 mPa·s to obtain the emulsion coating liquid. The weight ratio of the in-situ composite modified emulsion, alkylphenol polyoxyethylene ether, carboxymethyl cellulose, and neutral silica sol is 1000:6-6.5:4-4.3:8-8.5.

[0039] In this embodiment of the invention, preferably, the silica content of the neutral silica sol is 25-30 wt%.

[0040] In the preparation step of the emulsion coating solution in this embodiment of the invention, photographic gelatin, alkylphenol polyoxyethylene ether, carboxymethyl cellulose, neutral silica sol and modified emulsion are used in combination to further improve the compatibility of the emulsion coating solution with the microgravure coating process, improve the coating uniformity, and further optimize the mechanical properties of the emulsion layer of industrial X-ray film by combining the aforementioned raw materials (especially photographic gelatin and neutral silica sol), thereby optimizing the long-term stability of industrial X-ray film.

[0041] In this embodiment of the invention, the coating method further comprises using a micro-gravure coating process to coat the emulsion coating liquid onto the front and back surfaces of a PET substrate (polyethylene terephthalate substrate), controlling the single-sided coating thickness of the emulsion coating liquid to be 8-10 μm; then, a release layer coating liquid and a protective layer coating liquid are sequentially coated on the outer surface of the emulsion layer to obtain an industrial X-ray film; The isolation layer coating liquid includes alkylphenol polyoxyethylene ether, glutaraldehyde, deionized water, and gelatin; The protective coating liquid includes alkylphenol polyoxyethylene ether, silicone oil, glutaraldehyde, deionized water, and gelatin.

[0042] In the coating and molding step of this invention, by selecting a specific raw material composition for the isolation layer coating liquid and the protective layer coating liquid, the coating liquid is applied to the outer surface of the emulsion layer to form an isolation layer and a protective layer, thereby further optimizing the mechanical properties of the emulsion layer of the industrial X-ray film and thus optimizing the long-term stability of the industrial X-ray film.

[0043] In this embodiment of the invention, preferably, the coating amount of the isolation layer coating liquid on one side is 0.4-0.5 g / m². 2 ; The coating amount of the protective layer coating liquid on one side is 0.8-1 g / m². 2 .

[0044] In a preferred embodiment of the present invention, the isolation layer coating liquid is prepared by uniformly mixing alkylphenol polyoxyethylene ether, glutaraldehyde, and deionized water, and then adjusting the viscosity to 12-18 mPa·s using photographic gelatin. The weight ratio of the alkylphenol polyoxyethylene ether, glutaraldehyde, and deionized water is 6-6.5:1.8-2.2:1000.

[0045] In a preferred embodiment of the present invention, the protective coating liquid is prepared by uniformly mixing alkylphenol polyoxyethylene ether, silicone oil, and glutaraldehyde, and then adjusting the viscosity to 12-18 mPa·s using photographic gelatin. The weight ratio of the alkylphenol polyoxyethylene ether, silicone oil, glutaraldehyde, and deionized water is 6-6.5:10-11:3.5-4:1000.

[0046] The present invention also provides an industrial X-ray film prepared by the aforementioned method, wherein the upper and lower surfaces of the industrial X-ray film, from near to far, include: an emulsion layer, an isolation layer, and a protective layer; the emulsion layer is formed by coating with an emulsion coating liquid; the isolation layer is formed by coating with an isolation layer coating liquid; and the protective layer is formed by coating with a protective layer coating liquid.

[0047] The present invention will be further described below with reference to some specific embodiments.

[0048] Example 1 This embodiment provides a method for preparing industrial X-ray film, specifically: 1. Preparation of silver halide cubic particle emulsion Deionized water was introduced into a stirred reactor, and the stirring was started. The temperature was raised to 55°C, and photographic gelatin, polyvinylpyrrolidone (molecular weight 50,000), and sodium dioctyl succinate sulfonate were added while maintaining the temperature. After stirring for 35 minutes, the pH of the material was adjusted to 5.5 and the pAg of the material was adjusted to 7.43. Then, under stirring at 55°C, a 2.9 mol / L silver nitrate solution and a 2.95 mol / L potassium bromide solution were added dropwise simultaneously using a double-injection method. First, the concentrations of silver nitrate solution and potassium bromide solution were controlled. The dropping rate of the liquid was kept constant at 4 mL / min. After the first addition, the dropping was stopped after 6 min, and the mixture was kept warm and stirred for 20 min. Then, the initial dropping rate of the silver nitrate solution and potassium bromide solution was controlled at 2 mL / min, the acceleration of the dropping rate was 1.2 mL / min, and the final dropping rate was 30 mL / min. After the second addition, the dropping was stopped after 55 min, and the mixture was kept warm and stirred for 25 min to obtain a silver halide cubic particle emulsion with an equivalent circular diameter of 0.26 μm and a size variation coefficient of 7.3%.

[0049] The weight ratio of deionized water, photographic gelatin, polyvinylpyrrolidone, and sodium dioctyl succinate sulfonate is 950:50:4.5:0.2.

[0050] The total volume ratio of deionized water to the added silver nitrate solution is 1:1.1.

[0051] The total volume ratio of deionized water to the added potassium bromide solution is 1:1.1.

[0052] 2. In-situ composite modification At 55℃, the pH of the silver halide cubic particle emulsion was adjusted to neutral. Then, under stirring, a 0.1 mol / L zinc nitrate hexahydrate aqueous solution was added dropwise at a rate of 1.5 mL / min. After the addition was complete, the mixture was kept at the temperature and stirred for 15 min. Then, a 0.3 mol / L 2-methylimidazole aqueous solution was added dropwise at a rate of 0.7 mL / min. After the addition was complete, the mixture was allowed to cool naturally to 32℃ and stirred for 3 h to obtain the reaction solution. The reaction solution was then subjected to ultrafiltration, with the molecular weight cutoff controlled at 50 kDa. The ultrafiltration was carried out until the original volume of the reaction solution was 65%, thus obtaining the in-situ composite ZIF-8 modified emulsion.

[0053] The volume ratio of the silver halide cubic particle emulsion, the zinc nitrate hexahydrate aqueous solution, and the 2-methylimidazole aqueous solution is 100:23:23.

[0054] 3. Preparation of emulsion coating solution Under a water bath heating condition of 45℃, alkylphenol polyoxyethylene ether, carboxymethyl cellulose, and neutral silica sol (silica content 25wt%) were added to the modified emulsion. After stirring for 20 minutes, pre-swollen photographic gelatin was added to adjust the viscosity to 16 mPa·s to obtain the emulsion coating solution.

[0055] The weight ratio of the in-situ composite modified emulsion, alkylphenol polyoxyethylene ether, carboxymethyl cellulose, and neutral silica sol is 1000:6:4:8.

[0056] 4. Coating and molding Using a micro-gravure coating process, an emulsion coating liquid is applied to both sides of a PET substrate to form an emulsion layer, with the coating thickness controlled at 10 μm. Then, an isolation layer coating liquid and a protective layer coating liquid are sequentially applied to the outer surface of the emulsion layer to form an isolation layer and a protective layer, thus producing an industrial X-ray film.

[0057] The isolation layer coating solution was prepared at 40℃ by adding alkylphenol polyoxyethylene ether, glutaraldehyde, and deionized water in a weight ratio of 6:1.8:1000. After stirring until homogeneous, pre-swollen photographic gelatin was added to adjust the viscosity to 16 mPa·s. During the coating process, the single-sided coating amount of the isolation layer coating solution was controlled to be 0.5 g / m². 2 .

[0058] The protective coating solution was prepared at 40℃ by mixing alkylphenol polyoxyethylene ether, silicone oil, glutaraldehyde, and deionized water in a weight ratio of 6:10:3.5:1000. The alkylphenol polyoxyethylene ether, silicone oil, and glutaraldehyde were added to deionized water and stirred until homogeneous. Pre-swollen photographic gelatin was then added to adjust the viscosity to 16 mPa·s. During the coating process, the single-sided coating amount of the protective coating solution was controlled to be 0.9 g / m². 2 .

[0059] This embodiment also provides an industrial X-ray film prepared using the aforementioned method.

[0060] Example 2 This embodiment provides a method for preparing industrial X-ray film, specifically: 1. Preparation of silver halide cubic particle emulsion Deionized water was introduced into a stirred reactor, and the stirring was started. The temperature was raised to 58°C, and photographic gelatin, polyvinylpyrrolidone (molecular weight 50,000), and sodium dioctyl succinate sulfonate were added while maintaining the temperature. After stirring for 35 minutes, the pH of the material was adjusted to 5.5 and the pAg of the material was adjusted to 7.43. Then, under stirring at 58°C, a 3 mol / L silver nitrate solution and a 3.05 mol / L potassium bromide solution were added dropwise simultaneously using a double-injection method. First, the addition of the silver nitrate solution and the potassium bromide solution was controlled. The rate was kept constant at 4.2 mL / min. After the first addition was performed for 5.5 min, the addition was stopped, and the mixture was kept warm and stirred for 18 min. Then, the initial dropping rate of the silver nitrate solution and potassium bromide solution was controlled at 2.1 mL / min, the acceleration of the dropping rate was 1.2 mL / min, and the final dropping rate was 31 mL / min. After the second addition was performed for 53 min, the addition was stopped, and the mixture was kept warm and stirred for 20 min to obtain a silver halide cubic particle emulsion with an equivalent circular diameter of 0.27 μm and a size variation coefficient of 7.1%.

[0061] The weight ratio of deionized water, photographic gelatin, polyvinylpyrrolidone, and sodium dioctyl succinate sulfonate is 950:51:4.7:0.23.

[0062] The total volume ratio of deionized water to the added silver nitrate solution is 1:1.1.

[0063] The total volume ratio of deionized water to the added potassium bromide solution is 1:1.1.

[0064] 2. In-situ composite modification At 58℃, the pH of the silver halide cubic particle emulsion was adjusted to neutral. Then, under stirring, a 0.11 mol / L zinc nitrate hexahydrate aqueous solution was added dropwise at a rate of 1.7 mL / min. After the addition was complete, the mixture was kept at the temperature and stirred for 20 min. Then, a 0.33 mol / L 2-methylimidazole aqueous solution was added dropwise at a rate of 0.8 mL / min. After the addition was complete, the mixture was allowed to cool naturally to 33℃ and stirred for 3.5 h to obtain the reaction solution. The reaction solution was then subjected to ultrafiltration, with the molecular weight cutoff controlled at 50 kDa. Ultrafiltration was carried out until the original volume of the reaction solution was 65%, thus obtaining the in-situ composite ZIF-8 modified emulsion.

[0065] The volume ratio of the silver halide cubic particle emulsion, the zinc nitrate hexahydrate aqueous solution, and the 2-methylimidazole aqueous solution is 100:24:24.

[0066] 3. Preparation of emulsion coating solution Under a water bath heating condition of 48℃, alkylphenol polyoxyethylene ether, carboxymethyl cellulose, and neutral silica sol (silica content 25wt%) were added to the modified emulsion. After stirring for 25 minutes, pre-swollen photographic gelatin was added to adjust the viscosity to 16 mPa·s to obtain the emulsion coating solution.

[0067] The weight ratio of the in-situ composite modified emulsion, alkylphenol polyoxyethylene ether, carboxymethyl cellulose, and neutral silica sol is 1000:6.3:4.1:8.2.

[0068] 4. Coating and molding Using a micro-gravure coating process, an emulsion coating liquid is applied to both sides of a PET substrate to form an emulsion layer, with the coating thickness controlled at 10 μm. Then, an isolation layer coating liquid and a protective layer coating liquid are sequentially applied to the outer surface of the emulsion layer to form an isolation layer and a protective layer, thus producing an industrial X-ray film.

[0069] The isolation layer coating solution was prepared at 42℃ by adding alkylphenol polyoxyethylene ether, glutaraldehyde, and deionized water in a weight ratio of 6.3:2:1000. After stirring until homogeneous, pre-swollen photographic gelatin was added to adjust the viscosity to 16 mPa·s. During the coating process, the single-sided coating amount of the isolation layer coating solution was controlled to be 0.5 g / m². 2 .

[0070] The protective coating solution was prepared at 42℃ by adding alkylphenol polyoxyethylene ether, silicone oil, glutaraldehyde, and deionized water in a weight ratio of 6.3:10.5:3.8:1000. After stirring until homogeneous, pre-swollen photographic gelatin was added to adjust the viscosity to 16 mPa·s. The coating amount was controlled at 0.9 g / m² on each side during the coating process. 2 .

[0071] This embodiment also provides an industrial X-ray film prepared using the aforementioned method.

[0072] Example 3 This embodiment provides a method for preparing industrial X-ray film, specifically: 1. Preparation of silver halide cubic particle emulsion Deionized water was introduced into a stirred reactor, and the stirring was started. The temperature was raised to 60°C, and photographic gelatin, polyvinylpyrrolidone (molecular weight 50,000), and sodium dioctyl succinate sulfonate were added while maintaining the temperature. After stirring for 40 minutes, the pH of the material was adjusted to 5.5 and the pAg was adjusted to 7.43. Then, under stirring at 60°C, a 3.1 mol / L silver nitrate solution and a 3.15 mol / L potassium bromide solution were added dropwise simultaneously using a double-injection method. First, the concentrations of the silver nitrate solution and the potassium bromide solution were controlled. The dropping rate was kept constant at 4.5 mL / min. After the first addition, the dropping was stopped after 5 min, and the mixture was kept warm and stirred for 15 min. Then, the initial dropping rate of the silver nitrate solution and potassium bromide solution was controlled at 2.2 mL / min, the acceleration of the dropping rate was 1.3 mL / min, and the final dropping rate was 32 mL / min. After the second addition, the dropping was stopped after 50 min, and the mixture was kept warm and stirred for 25 min to obtain a silver halide cubic particle emulsion with an equivalent circular diameter of 0.30 μm and a size variation coefficient of 7.6%.

[0073] The weight ratio of deionized water, photographic gelatin, polyvinylpyrrolidone, and sodium dioctyl succinate sulfonate is 950:52:4.8:0.25.

[0074] The total volume ratio of deionized water to the added silver nitrate solution is 1:1.2.

[0075] The total volume ratio of deionized water to the added potassium bromide solution is 1:1.2.

[0076] 2. In-situ composite modification At 60℃, the pH of the silver halide cubic particle emulsion was adjusted to neutral. Then, under stirring, a 0.12 mol / L zinc nitrate hexahydrate aqueous solution was added dropwise at a rate of 2 mL / min. After the addition was complete, the mixture was kept at the temperature and stirred for 30 min. Then, a 0.36 mol / L 2-methylimidazole aqueous solution was added dropwise at a rate of 1 mL / min. After the addition was complete, the mixture was allowed to cool naturally to 35℃ and stirred for 4 h to obtain the reaction solution. The reaction solution was then subjected to ultrafiltration, with the molecular weight cutoff controlled at 50 kDa. The ultrafiltration was carried out until the original volume of the reaction solution was 65%, thus obtaining the in-situ composite ZIF-8 modified emulsion.

[0077] The volume ratio of the silver halide cubic particle emulsion, the zinc nitrate hexahydrate aqueous solution, and the 2-methylimidazole aqueous solution is 100:25:25.

[0078] 3. Preparation of emulsion coating solution Under a water bath heating condition of 50℃, alkylphenol polyoxyethylene ether, carboxymethyl cellulose, and neutral silica sol (silica content 25wt%) were added to the modified emulsion. After stirring for 30 minutes, pre-swollen photographic gelatin was added to adjust the viscosity to 16 mPa·s to obtain the emulsion coating solution.

[0079] The weight ratio of the in-situ composite modified emulsion, alkylphenol polyoxyethylene ether, carboxymethyl cellulose, and neutral silica sol is 1000:6.5:4.3:8.5.

[0080] 4. Coating and molding Using a micro-gravure coating process, an emulsion coating liquid is applied to both sides of a PET substrate to form an emulsion layer, with the coating thickness controlled at 10 μm. Then, an isolation layer coating liquid and a protective layer coating liquid are sequentially applied to the outer surface of the emulsion layer to form an isolation layer and a protective layer, thus producing an industrial X-ray film.

[0081] The isolation layer coating solution was prepared at 45℃ by adding alkylphenol polyoxyethylene ether, glutaraldehyde, and deionized water in a weight ratio of 6.5:2.2:1000. After stirring until homogeneous, pre-swollen photographic gelatin was added to adjust the viscosity to 16 mPa·s. During the coating process, the single-sided coating amount of the isolation layer coating solution was controlled to be 0.5 g / m². 2 .

[0082] The protective coating solution was prepared at 45℃ by mixing alkylphenol polyoxyethylene ether, silicone oil, glutaraldehyde, and deionized water in a weight ratio of 6.5:11:4:1000. The alkylphenol polyoxyethylene ether, silicone oil, and glutaraldehyde were added to deionized water and stirred until homogeneous. Pre-swollen photographic gelatin was then added to adjust the viscosity to 16 mPa·s. During the coating process, the single-sided coating amount of the protective coating solution was controlled to be 0.9 g / m². 2 .

[0083] This embodiment also provides an industrial X-ray film prepared using the aforementioned method.

[0084] Comparative Example 1 For ease of comparison, Comparative Example 1 adopts the technical solution of Example 2, the difference being: 1) in the preparation of silver halide cubic particle emulsion, the addition of polyvinylpyrrolidone (molecular weight 50000) and sodium dioctyl succinate sulfonate is omitted; 2) in the step of preparing emulsion coating liquid, the addition of alkylphenol polyoxyethylene ether and neutral silica sol (silica content 25wt%) is omitted.

[0085] In the preparation of the silver halide cubic particle emulsion in Comparative Example 1, the equivalent circle diameter of the prepared silver halide cubic particles was 0.35 μm, and the coefficient of variation of size was 9.9%.

[0086] Comparative Example 2 For ease of comparison, Comparative Example 2 adopts the technical solution of Example 2, the difference being that: the in-situ composite modification step is omitted, and the silver halide cubic particle emulsion obtained in the previous step is directly used in the subsequent preparation of the emulsion coating liquid.

[0087] The background fog density D0 and modulation transfer function MTF of the industrial X-ray films of Examples 1-3 and Comparative Examples 1-2 were respectively measured. 50 Average slope G, relative sensitivity S, exposure latitude L, maximum density D max Contrast coefficient γ, specific sensitivity S R The scratch resistance was tested, and the specific results are shown in the table below:

[0088] Furthermore, the industrial X-ray films of Examples 2 and 1-2 were placed in a constant temperature and humidity environment of 55°C and 85% for 28 days of static storage. The background haze density of each industrial X-ray film was then measured, and the background haze density increment ΔD0 was calculated. The calculation method for the background haze density increment ΔD0 is: background haze density after static storage - background haze density before static storage. The specific results are shown in the table below:

[0089] Furthermore, at room temperature, 50 N / cm was applied to the industrial X-ray films of Example 2 and Comparative Examples 1-2, respectively. 2 The pressure was used to conduct a pressure environment simulation test; after maintaining the aforementioned pressure for 6 hours, the background fog density of each industrial X-ray film was measured, and the background fog density increment ΔD0 was calculated. The calculation method for the background fog density increment ΔD0 is the same as the method described above. The specific results are shown in the table below:

[0090] As can be seen, in the preparation of industrial X-ray films in Examples 1-3, the preparation of silver halide cubic particle emulsion involves the use of polyvinylpyrrolidone, sodium dioctyl succinate sulfonate, and a double-injection process. The composite stabilizing system composed of polyvinylpyrrolidone and sodium dioctyl succinate effectively achieves uniform nucleation and controllable growth of silver halide cubic particles through the steric hindrance and electrostatic stabilization of the particle preparation material. This results in uniformly sized silver halide cubic particles, reducing image graininess and improving image resolution. Simultaneously, in the in-situ composite modification step, zinc nitrate aqueous solution and 2-methylimidazole aqueous solution are sequentially added to the silver halide cubic particle emulsion. Through in-situ composite, a metal-organic framework (ZIF-8) is further composited onto the silver halide cubic particles. The ZIF-8 isolates each silver halide cubic particle, inhibiting the lateral migration of silver atoms and the merging of development centers between adjacent particles during development. This improves the image edge blurring caused by silver diffusion, enhances image edge sharpness, further improves the image resolution and photosensitivity of industrial X-ray film, broadens its dynamic range, and enhances its long-term stability. The aforementioned techniques work synergistically to effectively overcome the problems of significant image graininess, lateral silver atom migration, and merging of development centers between adjacent particles. While improving image resolution, it also increases the utilization rate of X-ray photons, effectively improving photosensitivity and photosensitivity response range; and enhances the long-term stability of industrial X-ray film, especially its pressure stability and environmental stability.

[0091] As shown in Comparative Example 1, omitting polyvinylpyrrolidone and sodium dioctyl succinate sulfonate in the preparation of the silver halide cubic particle emulsion, and omitting alkylphenol polyoxyethylene ether and neutral silica sol in the preparation of the emulsion coating solution, resulted in a certain degree of deterioration in the particle size and dimensional stability of the obtained silver halide cubic particles due to the lack of effective control over the material system and preparation process of the silver halide cubic particles by polyvinylpyrrolidone and sodium dioctyl succinate sulfonate. Simultaneously, the lack of optimization of alkylphenol polyoxyethylene ether and neutral silica sol in the emulsion coating solution step reduced the compatibility of the emulsion coating solution with the microgravure coating process, and decreased the stability of the emulsion layer itself. These combined effects led to a certain degree of reduction in the image resolution, photosensitivity, photosensitivity range, scratch resistance, and long-term stability of the industrial X-ray film.

[0092] As can be seen from Comparative Example 2, when the in-situ composite modification step (i.e., the composite metal-organic framework ZIF-8) is omitted in the preparation of industrial X-ray film, the lack of the isolation, sensitization and chemical crosstalk protection effects of ZIF-8 on each silver halide cubic particle directly leads to a significant reduction in the image resolution, photosensitivity, photosensitivity response range and long-term stability of industrial X-ray film.

[0093] Unless otherwise stated, all percentages used in this invention are mass percentages.

[0094] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing industrial X-ray film, characterized in that, The process includes the following steps: preparing silver halide cubic particle emulsion, in-situ composite modification, preparing emulsion coating solution, and coating and molding. The method for preparing silver halide cubic particle emulsion is as follows: photographic gelatin, polyvinylpyrrolidone, and sodium dioctyl succinate sulfonate are added to deionized water and mixed evenly. The pH is then adjusted to 5.5 and pAg to 7.

43. Silver nitrate solution and potassium bromide solution are added dropwise at a temperature of 55-60℃. After the addition is complete, the mixture is kept warm and stirred to obtain silver halide cubic particle emulsion. The in-situ composite modification method is as follows: under a temperature of 55-60℃, the pH of the silver halide cubic particle emulsion is adjusted to neutral, and zinc nitrate aqueous solution and 2-methylimidazole aqueous solution are added dropwise in sequence; after the addition is completed, the mixture is kept at 32-35℃ and stirred to obtain a reaction solution; the reaction solution is subjected to ultrafiltration treatment until it is reduced to 64-67% of its original volume to obtain the modified emulsion of in-situ composite ZIF-8. The method for preparing the emulsion coating solution is as follows: at a temperature of 45-50℃, alkylphenol polyoxyethylene ether, carboxymethyl cellulose, and neutral silica sol are added to the modified emulsion and mixed evenly. Then, photographic gelatin is added to adjust the viscosity to 12-18 mPa·s to obtain the emulsion coating solution. Industrial X-ray films are prepared by coating and molding the emulsion layer using the aforementioned coating liquid.

2. The method for preparing industrial X-ray film according to claim 1, characterized in that, In the preparation of the silver halide cubic particle emulsion, the weight ratio of deionized water, photographic gelatin, polyvinylpyrrolidone, and sodium dioctyl succinate sulfonate is 950:50-52:4.5-4.8:0.2-0.

25. The total volume ratio of deionized water to the added silver nitrate solution is 1:1.1-1.2; The total volume ratio of deionized water to the added potassium bromide solution is 1:1.1-1.

2.

3. The method for preparing industrial X-ray film according to claim 1, characterized in that, In the preparation of the silver halide cubic particle emulsion, the molecular weight of polyvinylpyrrolidone is 45,000-55,000. The concentration of silver nitrate solution is 2.9-3.1 mol / L, and the concentration of potassium bromide solution is 2.95-3.15 mol / L.

4. The method for preparing industrial X-ray film according to claim 1, characterized in that, In the preparation of the silver halide cubic particle emulsion, under the temperature condition of 55-60℃, the dropping rate of silver nitrate solution and potassium bromide solution is first controlled to be constant at 4-4.5 mL / min for the first dropping, and then the temperature is maintained and stirred after the first dropping is completed. Then, the initial dropping rate of silver nitrate solution and potassium bromide solution was controlled at 2-2.2 mL / min, and the acceleration of the dropping rate was 1.2-1.3 mL / min. 2 The final dropping rate was 30-32 mL / min. A second dropping was then performed. After the second dropping was completed, the mixture was kept warm and stirred to obtain a silver halide cubic particle emulsion.

5. The method for preparing industrial X-ray film according to claim 4, characterized in that, The first addition should take 5-6 minutes, and the subsequent warming and stirring should take 15-20 minutes. The second addition should be done in 50-55 minutes, and the subsequent warming and stirring time should be 15-25 minutes.

6. The method for preparing industrial X-ray film according to claim 1, characterized in that, In the in-situ composite modification, the dropping rate of the zinc nitrate aqueous solution is 1.5-2 mL / min; The dropping rate of 2-methylimidazole aqueous solution is 0.7-1 mL / min; After the addition is complete, maintain the temperature at 32-35℃ and stir for 3-4 hours. The molecular weight cutoff for ultrafiltration is 50-60 kDa.

7. The method for preparing industrial X-ray film according to claim 1, characterized in that, In the in-situ composite modification, the concentration of the zinc nitrate aqueous solution is 0.1-0.12 mol / L; The concentration of 2-methylimidazole aqueous solution is 0.3-0.36 mol / L; The volume ratio of silver halide cubic particle emulsion, zinc nitrate aqueous solution, and 2-methylimidazole aqueous solution is 100:23-25:23-25.

8. The method for preparing industrial X-ray film according to claim 1, characterized in that, In the preparation of the emulsion coating solution, the weight ratio of modified emulsion, alkylphenol polyoxyethylene ether, carboxymethyl cellulose, and neutral silica sol is 1000:6-6.5:4-4.3:8-8.

5.

9. The method for preparing industrial X-ray film according to claim 1, characterized in that, The coating method involves using a micro-gravure coating process to coat the emulsion coating liquid onto both sides of the substrate, controlling the single-sided coating thickness of the emulsion coating liquid to be 8-10 μm; then, an isolation layer coating liquid and a protective layer coating liquid are sequentially coated on the outer surface of the emulsion layer to obtain an industrial X-ray film. The isolation layer coating liquid includes alkylphenol polyoxyethylene ether, glutaraldehyde, deionized water, and gelatin; The protective coating liquid includes alkylphenol polyoxyethylene ether, silicone oil, glutaraldehyde, deionized water, and gelatin.

10. An industrial X-ray film, characterized in that, It is prepared by the preparation method according to any one of claims 1-9.

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