Shrinkage rate measuring method and shrinkage rate measuring system for photo-thermal dual-curing material

Abstract

The invention discloses a method and a system for measuring the shrinkage rate of a photo-thermal dual-curing material, and relates to the technical field of material measurement, the method comprises the following steps: coating the surface of a flat substrate with an uncured photo-thermal dual-curing material; preparing a test thin film square block on the surface of the flat substrate, and calculating the volume of the uncured test thin film square block to obtain the volume of an uncured thin film; carrying out photocuring treatment on the test thin film square block to obtain a photocured test thin film square block, and calculating the volume of the photocured test thin film square block to obtain the volume of a photocured thin film; carrying out thermocuring treatment on the photocured test thin film square block to obtain a thermocured test thin film square block, and calculating the volume of the thermocured test thin film square block to obtain the volume of a thermocured thin film; and obtaining the target curing shrinkage rate of the photo-thermal dual-curing material according to the volume of the uncured film, the volume of the photo-cured film and the volume of the thermocured film. And the measurement precision and the measurement efficiency are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of material measurement, and in particular to a shrinkage measurement method and a shrinkage measurement system for a photothermal dual-curing material. Background Art

[0002] Photothermal dual-curing materials are a type of material that can be cured through the dual effects of light and heat. This type of material achieves the effects of rapid material curing, increased cross-linking density, and improved mechanical properties through the continuous or combined use of photocuring and thermal curing stages. It is widely used in integrated circuit manufacturing, precision electronic packaging, and microelectronic device coating. The accurate measurement of its curing shrinkage is directly related to the product's dimensional accuracy and structural reliability.

[0003] The traditional PVT method (pressure-volume-temperature method) can measure the volume change of bulk materials. However, for dual-curing materials, due to the limited penetration depth of ultraviolet light (UV light), the bulk material cannot be completely cured internally, and there is a difference between the measurement device and the actual process scene, resulting in inaccurate measurement of curing shrinkage rate; at the same time, the existing technology is difficult to achieve separate measurement of the shrinkage rate of the dual stages of light curing and thermal curing, and the measurement process is complicated and time-consuming, which restricts the efficiency of material research and development and process optimization.

[0004] Therefore, how to improve the measurement accuracy and efficiency of the curing shrinkage rate of photothermal dual-curing materials is a technical problem that needs to be solved urgently. Summary of the invention

[0005] The present invention provides a shrinkage measurement method and a shrinkage measurement system for a photothermal dual-curing material, so as to solve the technical problem that the measurement accuracy and efficiency of the curing shrinkage of the existing photothermal dual-curing material are low.

[0006] In a first aspect, a method for measuring shrinkage of a light-heat dual-curing material is provided, comprising: coating an uncured light-heat dual-curing material on a surface of a flat substrate; Preparing a test film block on the surface of the flat substrate, and calculating the volume of the uncured test film block to obtain the uncured film volume; Performing a photocuring treatment on the test film block to obtain a photocured test film block, and calculating the volume of the photocured test film block to obtain a photocured film volume; Performing heat curing treatment on the light-cured test film block to obtain a heat-cured test film block, and calculating the volume of the heat-cured test film block to obtain a heat-cured film volume; Based on the volume of the uncured film, the volume of the photocured film, and the volume of the thermally cured film, the target curing shrinkage rate of the photo-thermal dual-curing material is obtained.

[0007] In a second aspect, a shrinkage rate measurement system for a photo-thermal dual-curing material is provided. The shrinkage rate measurement system includes a testing device, a coating device, a flat substrate, a pattern exposure system, a photocuring device, and a thermal curing device. The coating device is used to coat the uncured photo-thermal dual-curing material on the surface of the flat substrate. The pattern exposure system is used to prepare a test film square on the surface of the flat substrate. The testing device is used to calculate the volume of the uncured test film square to obtain the volume of the uncured film. The photocuring device is used to perform photocuring treatment on the test film square to obtain a photocured test film square. The testing device is further used to calculate the volume of the photocured test film square to obtain the volume of the photocured film. The thermal curing device is used to perform thermal curing treatment on the photocured test film square to obtain a thermally cured test film square. The testing device is further used to calculate the volume of the thermally cured test film square to obtain the volume of the thermally cured film. The testing device is further used to obtain the target curing shrinkage rate of the photo-thermal dual-curing material based on the volume of the uncured film, the volume of the photocured film, and the volume of the thermally cured film.

[0008] A solution provided by the present invention is to coat an uncured photo-thermal dual-curing material on the surface of a flat substrate; prepare a test film square on the surface of the flat substrate, calculate the volume of the uncured test film square to obtain the volume of the uncured film; perform photo-curing treatment on the test film square to obtain a photo-cured test film square, and calculate the volume of the photo-cured test film square to obtain the volume of the photo-cured film; perform thermal-curing treatment on the photo-cured test film square to obtain a thermally-cured test film square, and calculate the volume of the thermally-cured test film square to obtain the volume of the thermally-cured film; according to the volume of the uncured film, the volume of the photo-cured film, and the volume of the thermally-cured film, obtain the target curing shrinkage rate of the photo-thermal dual-curing material. In this embodiment, the volume change of the test film square is measured in two stages of photo-curing and thermal-curing, the curing shrinkage rate of each stage is accurately calculated, and the overall curing shrinkage rate is further deduced, providing a systematic method for measuring the curing shrinkage rate, effectively solving the technical problems of low measurement accuracy and low measurement efficiency of the curing shrinkage rate of existing photo-thermal dual-curing materials, realizing the separate measurement of the shrinkage rates in the two stages of photo-curing and thermal-curing, and improving the measurement accuracy and measurement efficiency of photo-thermal dual-curing materials, providing an important scientific basis for the performance optimization and practical application of photo-thermal dual-curing materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments of the present invention will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention, and those of ordinary skill in the art can also obtain other drawings based on these drawings without creative efforts.

[0010] Figure 1 is a schematic diagram of measuring the curing shrinkage rate by the existing P-V-T method; Figure 2 is a flowchart of a method for measuring the shrinkage rate of a photo-thermal dual-curing material in an embodiment of the present invention; Figure 3 is a schematic diagram of a system for measuring the shrinkage rate of a photo-thermal dual-curing material in an embodiment of the present invention; Figure 4 is a 3D morphology schematic diagram of a test film square under the test of a white light interferometer in an embodiment of the present invention; Figure 5 is a schematic diagram of the thickness and width contour lines of a test film square under the test of a white light interferometer in an embodiment of the present invention; Figure 6 is a schematic diagram of the volume change data during the curing process of a photo-thermal dual-curing material in an embodiment of the present invention; Figure 7 This is a schematic diagram for statistical data of the volume change during the curing process of the photo-thermal dual-curing material in an embodiment of the present invention. Detailed implementation manners

[0011] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0012] It should be understood that the present invention can be implemented in different forms and should not be construed as limited to the embodiments set forth herein. On the contrary, providing these embodiments will make the disclosure thorough and complete, and will fully convey the scope of the present invention to those skilled in the art. In the drawings, for clarity, the dimensions and relative dimensions of layers and regions may be exaggerated. The same reference numerals denote the same elements throughout the drawings.

[0013] It should be understood that when an element or layer is referred to as "on", "adjacent to", "connected to" or "coupled to" another element or layer, it can be directly on, adjacent to, connected or coupled to the other element or layer, or there may be intervening elements or layers. In contrast, when an element is referred to as "directly on", "directly adjacent to", "directly connected to" or "directly coupled to" another element or layer, there are no intervening elements or layers. It should be understood that although the terms first, second, third, etc. may be used to describe various elements, components, regions, layers and / or parts, these elements, components, regions, layers and / or parts should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or part from another element, component, region, layer or part. Therefore, without departing from the teachings of the present invention, the first element, component, region, layer or part discussed below may be denoted as the second element, component, region, layer or part.

[0014] Spatial relationship terms such as "under", "below", "beneath", "underneath", "above", "over", etc. may be used herein for convenience of description to describe the relationship of one element or feature shown in the figures to other elements or features. It should be understood that, in addition to the orientation shown in the figures, spatial relationship terms are also intended to include different orientations of the device in use and operation. For example, if the device in the figures is flipped, then an element or feature described as "under other elements" or "beneath them" or "underneath them" will be oriented "above" the other elements or features. Thus, the exemplary terms "under" and "beneath" can include both an upper and a lower orientation. The device may be otherwise oriented (rotated 90 degrees or other orientations) and the spatial descriptors used herein are to be interpreted accordingly.

[0015] The purpose of the terms used herein is only to describe specific embodiments and is not a limitation of the present invention. As used herein, the singular forms "a", "an" and "the" are also intended to include the plural forms unless the context clearly dictates otherwise. It should also be understood that the terms "comprising" and / or "including", when used in this specification, specify the presence of the stated features, integers, steps, operations, elements and / or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components and / or groups. As used herein, the term "and / or" includes any and all combinations of the related listed items.

[0016] For a thorough understanding of the present invention, the related terms involved in the embodiments of the present invention and the existing measurement methods of curing shrinkage rate are introduced as follows.

[0017] The related terms involved in the present invention are introduced as follows: Photo-thermal dual-curing material: A photo-thermal dual-curing material refers to a material that can be cured simultaneously or sequentially by both photo-curing and thermal-curing methods; among them, photo-curing usually initiates a chemical reaction of the photosensitive functional groups in the material by ultraviolet light (UV light) irradiation to form a cross-linked network, enabling the material to rapidly transform from a liquid or semi-solid state to a solid state; thermal-curing, on the other hand, causes the thermosensitive functional groups in the material to react by heating, further improving the cross-linking density and mechanical properties of the material.

[0018] It should be understood that the advantages of this photo-thermal dual-curing material lie in its fast curing speed and flexible reaction control, which can adjust the properties of the material at different curing stages and are widely used in fields such as fine electronic components, integrated circuit manufacturing, and high-precision coatings. For example, the solder mask ink on the outermost layer of printed circuit boards (PCBs) and IC substrates is composed of a photo-thermal dual-curing material. Through exposure and development, it can expose the parts on the surface of the IC substrate that need to be connected to the chip and other electronic components in the subsequent backend process, and further enhance the structural stability in the subsequent photo-curing and thermal-curing stages. In the packaging industry, the photo-curing reaction of the photo-thermal dual-curing system adhesive can meet the requirements of the production line, while the thermal-curing ensures the durability and reliability of the bonding layer.

[0019] Cure Shrinkage Ratio: The Cure Shrinkage Ratio refers to the ratio of dimensional change caused by the volume shrinkage of the material during the curing process due to the chemical reaction between molecular chains to form a cross-linked structure, usually expressed as a percentage. Among them, the cure shrinkage ratio is an important parameter to measure the volume change of the material during curing, which affects the final dimensional stability, mechanical properties, and reliability of the material in applications.

[0020] For example, in industrial production, especially in the manufacturing of integrated circuit components, the cure shrinkage ratio of the material directly affects the dimensional accuracy and structural stability of the product. An excessively high cure shrinkage ratio may lead to an increase in internal stress within the material, thereby causing problems such as cracking, warping, or delamination between layers, affecting the electrical performance and mechanical strength of the product. In the field of materials research, the measurement and analysis of the cure shrinkage ratio provide important bases for the development and optimization of new materials. By studying the shrinkage behavior of materials under different curing conditions, researchers can optimize the material formula and regulate the cross-linking density, thereby improving the final performance of the material.

[0021] White Light Interferometer: A White Light Interferometer is a precision measuring instrument based on the interference principle. It uses the interference fringes generated by a broadband light source (white light) to perform high-precision measurements on the surface topography or thickness of a sample. That is, through the design of the beam splitting and interference optical paths, the light beam is divided into a reference beam and a measurement beam, and the two interfere on the surface of the sample. Since white light contains light of multiple wavelengths, it is possible to achieve measurements with nanometer-level precision by analyzing the interference fringes of light of different wavelengths. It is widely used in non-contact measurements of microscopic structures such as thin film thickness, surface roughness, and step height, and is particularly suitable for the fields of precision manufacturing and materials science.

[0022] The existing measurement methods for the cure shrinkage ratio are introduced as follows: Such as Figure 1As shown, the commonly used measurement methods for the curing shrinkage rate currently include the P-V-T (Pressure-Volume-Temperature) method (pressure-volume-temperature method). In this method, the material to be measured is placed in a sealed container, and the displacement of the piston in the container during the heating process is measured, and then the volume change of the material to be measured is deduced to calculate the curing shrinkage rate.

[0023] Please also refer to the present invention Figures 2 to 7 and the following specific embodiments to introduce in detail a method for measuring the shrinkage rate and a system for measuring the shrinkage rate of a photo-thermal dual-curing material provided by the present invention, so as to illustrate the technical solutions proposed by the present invention. The preferred embodiments of the present invention are described in detail below. However, in addition to these detailed descriptions, the present invention may also have other implementation manners.

[0024] In the first aspect, as Figure 2 and Figure 3 shown, a method for measuring the shrinkage rate of a photo-thermal dual-curing material is provided, including the following steps: S10. Coating the uncured photo-thermal dual-curing material on the surface of a flat substrate, where the photo-thermal dual-curing material is a material that is cured through the dual action of light and heat.

[0025] In this embodiment, the thickness of the flat substrate (substrate) is m - 1200 m. Preferably, the thickness of the flat substrate can be 500 m, m, m, m, 900 m, m or 1100 m. Selecting a relatively thick flat substrate here can effectively prevent the deformation of the test material (photo-thermal dual-curing material) during the curing process, and can be specifically selected according to needs. Here, it is only used as an example and does not constitute a limitation to the present invention; the surface roughness of the flat substrate is 0.3 m - m. Preferably, the surface roughness of the flat substrate can be m, m, m or 0.7 m, and can be specifically selected according to needs to ensure the stability in the subsequent steps. Here, it is only used as an example and does not constitute a limitation to the present invention.

[0026] The photo-thermal dual-curing material is a material that is cured through the dual action of light and heat. For example, solder resist ink, photo-thermal curable adhesive, photo-thermal curable coating, and photo-thermal curable resin for 3D printing, etc.

[0027] As an example, a glass substrate with a thickness of m and a surface roughness of 0.5 m and a size of 200 mm × 200 mm can be selected as the flat substrate, and solder mask ink can be selected as the photo-thermal dual-curing material; next, the solder mask ink can be evenly coated on the surface of the glass substrate by using a doctor blade coating technique. For example, a coating device (such as a doctor blade or other device) can be used to evenly coat the solder mask ink on the surface of the glass substrate to ensure that the thickness of the formed test film surface is uniform and meets the design requirements. Among them, the thickness of the coating device is m - m. Preferably, the thickness of the coating device can be m, 50 m, m, m, m or m. Here, it is only used as an example, and specifically can be selected according to needs, which does not constitute a limitation to the present invention. After coating, check whether the surface of the formed test film is flat, without bubbles or other defects, and ensure that the coating quality meets the standard. After the coating is completed, step S20 is entered.

[0028] It should be understood that the thickness of the uncured photo-thermal dual-curing material coated on the surface of the flat substrate does not exceed m. Preferably, the thickness of the uncured photo-thermal dual-curing material coated on the surface of the flat substrate can be m, m or 25 m. Here, it is only used as an example, which does not constitute a limitation to the present invention. By controlling the thickness of the uncured photo-thermal dual-curing material coated on the surface of the flat substrate within 30 m, it can be ensured that this thickness is within the light transmission depth, and it is ensured that the photo-thermal dual-curing material can fully react during the photo-curing stage.

[0029] S20. Prepare test film squares on the surface of the flat substrate, and calculate the volume of the uncured test film squares to obtain the volume of the uncured film.

[0030] In this embodiment, there are multiple test film squares (sample squares), for example, 16 - 100 test film squares. Among them, the test film squares can be distributed in an array on the surface of the flat substrate, for example, arranged in a 5 × 5 matrix. In addition, to ensure the measurement accuracy of the curing shrinkage rate, the side length or diameter of the test film squares can be m - m. Among them, the shape of the test film square can be rectangular, circular, etc., which is not limited here. Taking the shape of the test film square as rectangular as an example, preferably, the side length of the test film square can be m, m or 180 m, which is not limited here.

[0031] In one embodiment, that is, in the process of preparing the test film square on the surface of the flat substrate, the following steps are included: S20A. Use the exposure process and the development process to prepare the test film square on the surface of the flat substrate.

[0032] In this embodiment, the exposure process refers to using laser exposure to expose the photo-thermal dual-curing material to ultraviolet light or other light sources with appropriate wavelengths, so as to form a preset test film pattern on the surface of the photo-thermal dual-curing material. For example, use an exposure machine to project ultraviolet light onto the surface of the photo-thermal dual-curing material. The surface of the photo-thermal dual-curing material in the ultraviolet light irradiation area undergoes chemical changes, while the unirradiated area remains unchanged. By controlling the intensity of the light source and the exposure time, a preset test film pattern is formed.

[0033] The development process refers to using a developer to remove the unirradiated part and retain the exposed test film pattern, so as to obtain the test film square.

[0034] As an example, the coated flat substrate can be placed in an ultraviolet light exposure machine, and exposed using an ultraviolet light source with a wavelength of 365 nm, and the exposure time is controlled at 5 seconds to ensure that the surface of the photo-thermal dual-curing material can fully absorb ultraviolet light and initiate the photocuring reaction. After exposure, the uncured part outside the test film pattern is removed through the development process, leaving an array of test film squares. After development is completed, the surface of the test film square is dried to remove excess solvent and moisture, and finally an array of uniformly arranged test film squares is formed. Through the above steps, the size and shape of the test film square can be precisely controlled to ensure that the size and shape of each test film square are consistent, so as to ensure reliable volume measurement data in the subsequent steps.

[0035] In another embodiment, that is, in the process of calculating the volume of the uncured test film square to obtain the uncured film volume, the following steps are included: S21. Use a white light interferometer to measure the initial three-dimensional dimensions of the uncured test film square. The initial three-dimensional dimensions include the first height difference between the top surface of the uncured test film square and the surface of the flat substrate, and the length and width dimensions of the upper, middle, and lower parts of the uncured test film square; S22. Obtain the volume of the uncured film based on the first height difference and the length and width dimensions of the upper, middle, and lower parts of the uncured test film square.

[0036] In this embodiment, the length and width dimensions of the upper, middle, and lower parts of the uncured test film square refer to the length and width dimensions of the upper, middle, and lower parts of the uncured test film square. For example, an uncured rectangular test film square is equally divided into three parts in width, corresponding to the upper, middle, and lower parts of the uncured test film square respectively. Here, this is only an example and does not constitute a limitation to the present invention.

[0037] It should be understood that since there are slight differences in thickness or morphology at different parts of the uncured test film square, measuring the three parts can more accurately reflect the overall geometric characteristics of the uncured test film square.

[0038] As an example, a white light interferometer is used to measure the initial three-dimensional dimensions of the uncured test film square, that is, the white light interferometer is used to measure the length and width dimensions of the upper, middle, and lower parts of the uncured test film square respectively, and the first height difference between the top surface of the uncured test film square and the surface of the flat substrate. Next, the test device will calculate the volume of the uncured test film square based on the first height difference of the uncured test film square measured by the white light interferometer and the length and width dimensions of the upper, middle, and lower parts, and obtain the volume of the uncured film. Among them, when using the white light interferometer to test the uncured test film square, the 3D morphology of the uncured test film square shown on the white light interferometer is as Figure 4 shown, and the data shown during the measurement process is as Figure 5 shown. It should be noted that the above test device includes a personal computer, a laptop, a smartphone, a tablet computer, etc.

[0039] It should be understood that the first height here can include three height differences corresponding to the upper, middle, and lower parts of the uncured test film square respectively; it can also be one height difference. This is because in actual measurement, the three height differences are almost the same. Therefore, in order to improve the measurement efficiency, the first height differences of different parts of the same uncured test film square can be regarded as the same. Here, it does not constitute a limitation to the present invention.

[0040] Taking the first height difference of the same uncured test film square as being the same as an example, the volume of the uncured film of the uncured test film square can be calculated by the following formula: , , ; where, , , are the length and width dimensions of the upper, middle, and lower parts of the uncured test film square, respectively; is the third height difference (i.e., the height difference between the top surface of the uncured test film square and the surface of the flat substrate).

[0041] After calculating the volume of each region of the uncured test film square, the volumes of these regions are added together to obtain the volume of the uncured film of the uncured test film square, that is: .

[0042] For example, assume that the length and width dimensions of the upper, lower, and middle parts of the uncured test film square are m × m, m × m, and m × m, and the first height differences in the upper, middle, and lower parts are all regarded as m. According to these data and the above formula, the volume of the uncured film of each uncured test film square can be obtained.

[0043] Taking the first height including three height differences corresponding to the upper, middle, and lower parts of the uncured test film square as an example, the volume of the uncured film of the uncured test film square can be calculated by the following formula: , , ; wherein, , , are the length and width dimensions of the upper, middle, and lower parts of the uncured test film square, respectively; are the height differences corresponding to the upper, middle, and lower parts of the uncured test film square, respectively.

[0044] After calculating the volume of each region of the uncured test film square, the volumes of these regions are added together to obtain the volume of the uncured film of the uncured test film square, that is: .

[0045] For example, assume that the length and width dimensions of the upper, lower, and middle parts of the uncured test film square are m × m, m × m, and m × m, and the height difference in the upper part is m, the middle part is m, the lower part is m. According to these data and the above formula, the volume of the uncured film of each uncured test film square can be obtained.

[0046] It should be understood that the above is only an example and does not constitute a limitation to the present invention.

[0047] S30. Perform photocuring treatment on the test film square to obtain a photocured test film square, and calculate the volume of the photocured film of the photocured test film square.

[0048] As an example, performing photocuring treatment on the test film square to obtain a photocured test film square includes: placing the prepared uncured test film square that has been coated in an ultraviolet photocuring device (UV curing device) for photocuring treatment. For example, the light source wavelength of the ultraviolet photocuring device can be set to 365 nm, the power is 10 mW / cm², and the curing time is 10 minutes. During the photocuring process, ultraviolet light causes the photosensitive resin in the photo-thermal dual-curing material to undergo a chemical reaction, so that the structure of the uncured test film square crosslinks and cures, thereby obtaining a photocured test film square.

[0049] It should be noted that during the photocuring process, it should be ensured that the uncured test film square is uniformly and sufficiently irradiated during the photocuring process, so that the photo-thermal dual-curing material can complete the photocuring reaction to the greatest extent.

[0050] In one embodiment, that is, when calculating the volume of the photocured test film square to obtain the volume of the photocured film, the following steps are included: S31. Use a white light interferometer to measure the photocured three-dimensional dimensions of the photocured test film square. The photocured three-dimensional dimensions include the second height difference between the top surface of the photocured test film square and the surface of the flat substrate, and the length and width dimensions of the upper, middle, and lower parts of the photocured test film square; S32. Obtain the volume of the photocured film according to the second height difference and the length and width dimensions of the upper, middle, and lower parts of the photocured test film square.

[0051] It should be understood that the embodiments of steps S31 to S32 can refer to the descriptions of the embodiments of steps S21 to S22. The only differences here are the photo-cured three-dimensional dimensions and the initial three-dimensional dimensions, as well as the differences between the first height difference and the second height difference. The specific calculation processes are similar. To avoid repetition, they will not be elaborated here. It should be noted here that the measurement positions and methods of steps S31 to S32 should be consistent with those of steps S21 to S22 to ensure the accuracy of the subsequent calculation of the curing shrinkage rate.

[0052] S40. Perform thermal curing on the photo-cured test film square to obtain a thermally cured test film square, and calculate the volume of the thermally cured test film square to obtain the thermally cured film volume.

[0053] As an example, performing thermal curing on the photo-cured test film square to obtain a thermally cured test film square includes: placing the photo-cured film sample in a thermal curing device (such as an oven) for thermal curing. For example, the temperature of the thermal curing device can be set to 150 °C and the heat preservation time can be 30 minutes. During the thermal curing process, the thermosensitive functional groups in the photo-thermal dual-curing material undergo further cross-linking reactions, further improving the curing degree of the photo-thermal dual-curing material, thereby obtaining a thermally cured test film square.

[0054] It should be noted that during the photo-curing process, it should be ensured that the temperature distribution of the photo-cured test film square is uniform and the reaction is sufficient during the thermal curing process, so that the photo-thermal dual-curing material can complete the thermal curing reaction to the greatest extent.

[0055] In one embodiment, that is, in the process of calculating the volume of the thermally cured test film square to obtain the thermally cured film volume, the following steps are included: S41. Use a white light interferometer to measure the thermally cured three-dimensional dimensions of the thermally cured test film square. The thermally cured three-dimensional dimensions include the third height difference between the top surface of the thermally cured test film square and the surface of the flat substrate, and the length and width dimensions of the upper, middle, and lower parts of the thermally cured test film square. S42. Obtain the thermally cured film volume according to the third height difference and the length and width dimensions of the upper, middle, and lower parts of the thermally cured test film square.

[0056] It should be understood that the embodiments of steps S41 to S42 can refer to the descriptions of the embodiments of steps S21 to S22. The difference here lies only in the three-dimensional size of thermal curing and the initial three-dimensional size, as well as the differences between the first height difference and the third height difference. The specific calculation processes are similar. To avoid repetition, they will not be elaborated here. It should be noted that the measurement positions and methods of steps S41 to S42 should be consistent with those of steps S21 to S22 to ensure the accuracy of the subsequent calculation of the curing shrinkage rate.

[0057] In summary, through the above steps, the present invention realizes the separate measurement of the shrinkage rates in the photocuring and thermal curing stages, solves the problems that traditional methods usually require complex experimental equipment and operation steps and the measurement process is time-consuming, and avoids the problems that some photo-thermally dual-cured materials are in a semi-solid or high-viscosity state during the preparation process and cannot be measured in a P-V-T device, and that the actual use scenarios of some materials are not curing in a piston-shaped container, resulting in the measured curing shrinkage rate values not conforming to the actual situation, providing a data basis for the subsequent simultaneous calculation of the shrinkage rates in the photocuring and thermal curing stages.

[0058] S50. Obtain the target curing shrinkage rate of the photo-thermally dual-cured material according to the volume of the uncured film, the volume of the photocured film, and the volume of the thermally cured film.

[0059] In this embodiment, the target curing shrinkage rate of the photo-thermally dual-cured material includes the target photocuring shrinkage rate, the target thermal curing shrinkage rate, and the target overall volume shrinkage rate. For the convenience of introducing the subsequent embodiments, here the volume of the uncured film can be denoted as , the volume of the photocured film can be denoted as , and the volume of the thermally cured film can be denoted as .

[0060] As an example, the target photocuring shrinkage rate of the photo-thermally dual-cured material is calculated through step S51, that is: S51. Obtain the target photocuring shrinkage rate according to the volume of the uncured film and the volume of the photocured film.

[0061] As an example, the target photocuring shrinkage rate can be calculated through the following formula (1): Wherein, is the shrinkage rate during photocuring, representing the change ratio of the volume of the uncured film to the volume of the film after photocuring.

[0062] For example, as Figure 6 and Figure 7As shown, assuming that the volume of the uncured film of a certain test film square is 0.006 mm³ and the volume becomes 0.0058 mm³ after photocuring, the target photocuring shrinkage rate calculated by the above formula (1) is .

[0063] As another example, the target thermal curing shrinkage rate of the photo-thermal dual-curing material is calculated by step S52, that is: S52. Obtain the target thermal curing shrinkage rate according to the photocured film volume and the thermally cured film volume.

[0064] As an example, the target thermal curing shrinkage rate can be calculated by the following formula (2): Wherein, is the shrinkage rate during thermal curing, representing the change ratio of the volume of the film after photocuring to the volume of the film after thermal curing.

[0065] For example, as Figure 6 and Figure 7 shown, assuming that the volume of the photocured film of a certain test film square is 0.0058 mm³ and the volume after thermal curing is 0.0057 mm³, the target thermal curing shrinkage rate calculated by the above formula (2) is .

[0066] As another example, the target total volume shrinkage rate of the photo-thermal dual-curing material is calculated by step S53, that is: S53. Obtain the target total volume shrinkage rate according to the volume of the uncured film and the volume of the thermally cured film.

[0067] As an example, the target total volume shrinkage rate can be calculated by the following formula (3): Wherein, is the total shrinkage rate, representing the change ratio of the volume of the uncured film to the volume of the film after thermal curing.

[0068] For example, as Figure 6 and Figure 7 shown, assuming that the volume of the uncured film of a certain test film square is 0.006 mm³ and the volume after thermal curing is 0.0057 mm³, the target total volume shrinkage rate calculated by the above formula (3) is .

[0069] Through the above embodiments, the curing shrinkage rate of the photothermal dual-curing material at different stages can be accurately evaluated, providing accurate physical parameter support for the process design and application of the material. That is, the measurement of the photocuring shrinkage rate helps analyze the influence of the photocuring stage on the volume change of the test film square, ensuring the stability and uniformity of the material during the photocuring process; the measurement of the thermal curing shrinkage rate reveals the influence of the thermal curing stage on the further shrinkage of the test film square, providing data support for the final hardness and sealing performance of the material; the overall curing shrinkage rate can comprehensively evaluate the influence of the entire curing process on the performance of the test film square. Moreover, through the above embodiments, the measurement accuracy and reliability are improved, and the problem of inaccurate shrinkage rate measurement by the traditional P-V-T method is solved. This not only provides a theoretical basis for the development of new photothermal dual-curing materials but also helps optimize the curing process in actual production. For example, R & D personnel can optimize the process parameters of photocuring and thermal curing based on these data to ensure that the final product maintains sufficient strength and transparency after curing, thus avoiding deformation problems caused by excessive shrinkage and improving the final performance and application reliability of the material.

[0070] In summary, a solution provided by the present invention measures the volume change of the test film square in the photocuring and thermal curing stages respectively, accurately calculates the curing shrinkage rate of each stage, and further derives the overall curing shrinkage rate, providing a systematic method for measuring the curing shrinkage rate. This effectively solves the technical problems of low measurement accuracy and low measurement efficiency of the curing shrinkage rate of existing photothermal dual-curing materials, realizes the separate measurement of the shrinkage rates in the photocuring and thermal curing dual-stages, and improves the measurement accuracy and measurement efficiency of photothermal dual-curing materials, providing an important scientific basis for the performance optimization and practical application of photothermal dual-curing materials.

[0071] In one embodiment, that is, among steps S51 to S53, there are multiple test film squares, and each test film square corresponds to an uncured film volume, a photocured film volume, and a thermally cured film volume. In this embodiment, there are multiple test film squares, and each test film square corresponds to an uncured film volume, a photocured film volume, and a thermally cured film volume. To more accurately calculate the target photocuring shrinkage rate of the photothermal dual-curing material, the volume data corresponding to multiple test film squares can be weighted averaged, averaged, or by other means to obtain the target photocuring shrinkage rate, the target thermal curing shrinkage rate, and the target overall shrinkage rate, so as to comprehensively reflect the shrinkage characteristics of the photothermal dual-curing material at different curing stages. The following will be discussed in detail through steps S51A to S53A.

[0072] S51A. Obtain the target photocuring shrinkage rate based on the multiple uncured film volumes and the corresponding photocured film volumes.

[0073] As an example, based on the volumes of multiple uncured films and the corresponding volumes of photocured films, the target photocuring shrinkage rate is calculated, and the calculation formula is as shown in the following formula (4): Wherein, is the shrinkage rate during the photocuring process of the i-th test film square, is the volume of the uncured film of the i-th test film square, is the volume of the photocured film of the i-th test film square, n is the total number of test film squares.

[0074] Furthermore, the corresponding to multiple test film squares obtained by calculation and the total number of test film squares can be weighted averaged, averaged or in other ways to calculate the target photocuring shrinkage rate of the photo-thermo dual-curing material.

[0075] S52A. Obtain the target thermocuring shrinkage rate according to the volumes of multiple said photocured films and the corresponding volumes of thermocured films; As an example, based on the volumes of multiple photocured films and the corresponding volumes of thermocured films, the target thermocuring shrinkage rate is obtained, and the calculation formula is as shown in the following formula (5): Wherein, is the shrinkage rate during the thermocuring process of the i-th test film square, is the of the i-th test film square, is the of the i-th test film square, n is the total number of test film squares.

[0076] Furthermore, the corresponding to multiple test film squares obtained by calculation and the total number of test film squares can be weighted averaged, averaged or in other ways to calculate the target thermocuring shrinkage rate of the photo-thermo dual-curing material.

[0077] S53A. Obtain the target total volume shrinkage rate according to the volumes of multiple said uncured films and the corresponding volumes of thermocured films.

[0078] As an example, based on the volumes of multiple uncured films and the corresponding volumes of thermocured films, the target total volume shrinkage rate is obtained, and the calculation formula is as shown in the following formula (6): Wherein, is the shrinkage rate during the photocuring process of the i-th test film square, is the volume of the uncured film of the i-th test film square, is the volume of the thermally cured film of the i-th test film square, n is the total number of test film squares.

[0079] Furthermore, the calculated corresponding to multiple test film squares and the total number of test film squares can be weighted averaged, averaged or in other ways to calculate the of the dual photo-thermal curing material.

[0080] Through the above embodiments, the measurement accuracy of the shrinkage rate of the dual photo-thermal curing material is further improved. However, it should be noted that the above is only an example and does not constitute a limitation to the present invention.

[0081] In one embodiment, that is, after step S50, that is, after obtaining the target curing shrinkage rate according to the volume of the uncured film, the volume of the photocured film, and the volume of the thermally cured film, the following steps are included: S60. Obtain the target linear shrinkage rate of the dual photo-thermal curing material according to the relationship between the target curing shrinkage rate and the linear shrinkage rate.

[0082] In this embodiment, the target linear shrinkage rate includes the target light linear shrinkage rate, the target heat linear shrinkage rate, and the target overall linear shrinkage rate corresponding to the target curing shrinkage rate, that is, the target light linear shrinkage rate corresponding to the target photocuring shrinkage rate, the target heat linear shrinkage rate corresponding to the target thermocuring shrinkage rate, and the target overall linear shrinkage rate corresponding to the target overall volume shrinkage rate. Among them, the target light linear shrinkage rate characterizes the degree of linear shrinkage generated when the material is cured under the action of light, reflecting the influence of the photocuring process on the dimensional change of the material; the target heat linear shrinkage rate characterizes the linear shrinkage of the material when it is cured under the action of heat, reflecting the change of the material size during the thermocuring process; and the target overall linear shrinkage rate synthesizes the final linear shrinkage results of the material under the dual action of light and heat, which is the key index to measure the dimensional stability of the material during the entire dual photo-thermal curing process. Calculating these types of shrinkage rates from different angles together constitutes the target linear shrinkage rate, providing comprehensive data support for in-depth research and precise control of the curing shrinkage characteristics of the material.

[0083] As an example, after calculating the target curing shrinkage rate, further calculate the target linear shrinkage rate of the dual photo-thermal curing film material according to the relationship between the target curing shrinkage rate and the linear shrinkage rate. Specifically, there is a certain mathematical relationship between the curing shrinkage rate (i.e., volume shrinkage rate) and the linear shrinkage rate of the dual photo-thermal curing material, that is, it can be converted by formula (7): Among them, is the target solidification shrinkage rate, is the target linear shrinkage rate.

[0084] It should be understood that this formula assumes that the shrinkage behavior of the material during the solidification process presents a three-dimensional volume shrinkage mode. Therefore, the volume shrinkage rate is converted into a linear shrinkage rate by taking the cube root because the three-dimensional volume shrinkage of the material is usually closely related to the changes in its length, width, and height, and the linear shrinkage rate provides a measure of the length change in each direction.

[0085] Specifically, the target photocuring shrinkage rate can be converted into the corresponding target light linear shrinkage rate through the above formula (7), the target thermal curing shrinkage rate can be converted into the corresponding target heat linear shrinkage rate through the above formula (7), and the target overall volume shrinkage rate can be converted into the corresponding target overall linear shrinkage rate through the above formula (7). For example, the target photocuring shrinkage rate of a certain test film square is 3.3%. According to the above formula (7), the calculated target light linear shrinkage rate is about 1.1%; the target thermal curing shrinkage rate is , and according to the above formula (7), the calculated target heat linear shrinkage rate is about %; the target overall volume shrinkage rate is 5%, and according to the above formula (7), the calculated target overall linear shrinkage rate is about 1.6%. It should be understood that the above is only an example and does not constitute a limitation to the present invention.

[0086] By converting the target solidification shrinkage rate into the target linear shrinkage rate, the dimensional changes of the dual photocuring and thermal curing material during the solidification process can be understood more accurately. Especially for precision components or applications (such as high-end display protective films, optical thin film materials, etc.), the linear shrinkage rate is a more intuitive and crucial indicator. Therefore, through the above steps, it can effectively help manufacturers optimize the design and process flow to ensure the stability and dimensional accuracy of the final product, thereby improving the application performance and reliability of the material.

[0087] It should be noted that the shrinkage rate measurement method for the dual photocuring and thermal curing material provided by the present invention can not only be applied to the dual photocuring and thermal curing materials in the above-mentioned photocuring and thermal curing two-stage process, but also be applied to the shrinkage rate measurement of one or more hybrid curing materials, that is, including but not limited to the shrinkage rate measurement of one or more hybrid curing materials such as photocuring, thermal curing, and moisture curing, greatly expanding the practical value of this shrinkage rate measurement method in the field of material research and production.

[0088] It should be understood that the magnitudes of the sequence numbers of the steps in the above embodiments do not mean the order of execution. The order of execution of each process should be determined by its internal logic and should not constitute any limitation to the implementation process of the embodiments of the present invention.

[0089] Second aspect, asFigure 3 As shown, a shrinkage rate measurement system for a photo-thermal dual-curing material is provided. The shrinkage rate measurement system includes a test device, a coating device, a flat substrate, a graphic exposure system, a photo-curing device, and a thermal-curing device; The coating device is used to coat the uncured photo-thermal dual-curing material on the surface of the flat substrate; The graphic exposure system is used to prepare test film squares on the surface of the flat substrate; The test device is used to calculate the volume of the uncured test film square to obtain the uncured film volume; The photo-curing device is used to perform photo-curing treatment on the test film square to obtain a photo-cured test film square; The test device is also used to calculate the volume of the photo-cured test film square to obtain the photo-cured film volume; The thermal-curing device is used to perform thermal-curing treatment on the photo-cured test film square to obtain a thermally-cured test film square; The test device is also used to calculate the volume of the thermally-cured test film square to obtain the thermally-cured film volume; The test device is also used to obtain the target curing shrinkage rate of the photo-thermal dual-curing material according to the uncured film volume, the photo-cured film volume, and the thermally-cured film volume.

[0090] In one embodiment, the shrinkage rate measurement system further includes a white light interferometer; The white light interferometer is used to measure the initial three-dimensional dimensions of the uncured test film square. The initial three-dimensional dimensions include the first height difference between the top surface of the uncured test film square and the surface of the flat substrate, and the length and width dimensions of the upper, middle, and lower parts of the uncured test film square; The test device is also used to obtain the uncured film volume according to the first height difference and the length and width dimensions of the upper, middle, and lower parts of the uncured test film square.

[0091] In one embodiment, the white light interferometer is also used to measure the photo-cured three-dimensional dimensions of the photo-cured test film square. The photo-cured three-dimensional dimensions include the second height difference between the top surface of the photo-cured test film square and the surface of the flat substrate, and the length and width dimensions of the upper, middle, and lower parts of the photo-cured test film square; The test device is also used to obtain the photo-cured film volume according to the second height difference and the length and width dimensions of the upper, middle, and lower parts of the photo-cured test film square.

[0092] In one embodiment, the white light interferometer is further configured to measure the three-dimensional dimensions of the tested film square after thermal curing, where the three-dimensional dimensions after thermal curing include a third height difference between the top surface of the tested film square after thermal curing and the surface of the flat substrate, and the length and width dimensions of the upper, middle, and lower parts of the tested film square after thermal curing; The testing device is further configured to obtain the volume of the thermally cured film based on the third height difference and the length and width dimensions of the upper, middle, and lower parts of the tested film square after thermal curing.

[0093] In one embodiment, the target curing shrinkage rate of the photo-thermal dual-curing material includes a target photo-curing shrinkage rate, a target thermal-curing shrinkage rate, and a target overall volume shrinkage rate; The testing device is further configured to obtain the target photo-curing shrinkage rate based on the volume of the uncured film and the volume of the photo-cured film; The testing device is further configured to obtain the target thermal-curing shrinkage rate based on the volume of the photo-cured film and the volume of the thermally cured film; The testing device is further configured to obtain the target overall volume shrinkage rate based on the volume of the uncured film and the volume of the thermally cured film.

[0094] In one embodiment, there are multiple tested film squares; The testing device is further configured to obtain the target photo-curing shrinkage rate based on multiple volumes of the uncured film and the corresponding volumes of the photo-cured film; The testing device is further configured to obtain the target thermal-curing shrinkage rate based on multiple volumes of the photo-cured film and the corresponding volumes of the thermally cured film; The testing device is further configured to obtain the target overall volume shrinkage rate based on multiple volumes of the uncured film and the corresponding volumes of the thermally cured film.

[0095] In one embodiment, the testing device is further configured to obtain the target linear shrinkage rate of the photo-thermal dual-curing material based on the relationship between the target curing shrinkage rate and the linear shrinkage rate.

[0096] In one embodiment, the thickness of the uncured photo-thermal dual-curing material coated on the surface of the flat substrate does not exceed 30 m.

[0097] In one embodiment, the thickness of the flat substrate is 400 m - 1200 m, and the surface roughness is 0.3 m - 0.8 m.

[0098] It should be noted that the specific limitations of the shrinkage rate measurement system for the photothermal dual-curing material can be referred to the limitations of the shrinkage rate measurement method for the photothermal dual-curing material in the above text. To avoid repetition, it will not be elaborated here.

[0099] The above-described embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention, and should all be included in the protection scope of the present invention.

Claims

1. A method for measuring the shrinkage rate of a photothermal dual-curing material, characterized in that, Including: Coating an uncured photo-thermal dual-curing material on the surface of a flat substrate; Preparing a test film square on the surface of the flat substrate, and calculating the volume of the uncured test film square to obtain an uncured film volume; Performing photo-curing treatment on the test film square to obtain a photo-cured test film square, and calculating the volume of the photo-cured test film square to obtain a photo-cured film volume; Performing thermal-curing treatment on the photo-cured test film square to obtain a thermally-cured test film square, and calculating the volume of the thermally-cured test film square to obtain a thermally-cured film volume; Obtaining a target curing shrinkage rate of the photo-thermal dual-curing material according to the uncured film volume, the photo-cured film volume, and the thermally-cured film volume.

2. The shrinkage rate measurement method of the photothermal dual-curing material according to claim 1, characterized in that The calculating the volume of the uncured test film square to obtain an uncured film volume includes: Measuring the initial three-dimensional dimensions of the uncured test film square using a white light interferometer, where the initial three-dimensional dimensions include a first height difference between the top surface of the uncured test film square and the surface of the flat substrate, and the length and width dimensions of the upper, middle, and lower parts of the uncured test film square; Obtaining the uncured film volume according to the first height difference and the length and width dimensions of the upper, middle, and lower parts of the uncured test film square.

3. The shrinkage rate measurement method of the photo-thermal dual-curing material according to claim 1, wherein The calculating the volume of the photo-cured test film square to obtain a photo-cured film volume includes: Measuring the photo-cured three-dimensional dimensions of the photo-cured test film square using a white light interferometer, where the photo-cured three-dimensional dimensions include a second height difference between the top surface of the photo-cured test film square and the surface of the flat substrate, and the length and width dimensions of the upper, middle, and lower parts of the photo-cured test film square; Obtaining the photo-cured film volume according to the second height difference and the length and width dimensions of the upper, middle, and lower parts of the photo-cured test film square.

4. The shrinkage rate measurement method of the photothermal dual-curing material according to claim 1, characterized in that, The calculating the volume of the thermally-cured test film square to obtain a thermally-cured film volume includes: Measuring the thermally-cured three-dimensional dimensions of the thermally-cured test film square using a white light interferometer, where the thermally-cured three-dimensional dimensions include a third height difference between the top surface of the thermally-cured test film square and the surface of the flat substrate, and the length and width dimensions of the upper, middle, and lower parts of the thermally-cured test film square; Obtaining the thermally-cured film volume according to the third height difference and the length and width dimensions of the upper, middle, and lower parts of the thermally-cured test film square.

5. The shrinkage rate measurement method of the photothermal dual-curing material according to claim 1, characterized in that, The target curing shrinkage rate of the photo-thermal dual-curing material includes a target photo-curing shrinkage rate, a target thermal-curing shrinkage rate, and a target overall volume shrinkage rate; The obtaining the target curing shrinkage rate of the photo-thermal dual-curing material according to the uncured film volume, the photo-cured film volume, and the thermally-cured film volume includes: Obtaining the target photo-curing shrinkage rate according to the uncured film volume and the photo-cured film volume; Obtaining the target thermal-curing shrinkage rate according to the photo-cured film volume and the thermally-cured film volume; Based on the volume of the uncured film and the volume of the thermally cured film, the target overall volume shrinkage rate is obtained.

6. The method for measuring the shrinkage rate of the photo-thermal dual-curing material according to claim 5, characterized in that, There are multiple test film squares; The obtaining of the target photocuring shrinkage rate based on the volume of the uncured film and the volume of the photocured film includes: Based on the volumes of multiple uncured films and the corresponding volumes of the photocured films, the target photocuring shrinkage rate is obtained; The obtaining of the target thermal curing shrinkage rate based on the volume of the photocured film and the volume of the thermally cured film includes: Based on the volumes of multiple photocured films and the corresponding volumes of the thermally cured films, the target thermal curing shrinkage rate is obtained; The obtaining of the target overall volume shrinkage rate based on the volume of the uncured film and the volume of the thermally cured film includes: Based on the volumes of multiple uncured films and the corresponding volumes of the thermally cured films, the target overall volume shrinkage rate is obtained.

7. The shrinkage rate measurement method of the photothermal dual-curing material according to claim 1, characterized in that After obtaining the target curing shrinkage rate based on the volume of the uncured film, the volume of the photocured film, and the volume of the thermally cured film, it includes: Based on the relationship between the target curing shrinkage rate and the linear shrinkage rate, the target linear shrinkage rate of the photo-thermally dual-cured material is obtained.

8. The method for measuring the shrinkage rate of the photo-thermal dual-curing material according to any one of claims 1 to 7, characterized in that, The thickness of the uncured photo-thermal dual-curing material coated on the surface of the flat substrate does not exceed m.

9. The method for measuring the shrinkage rate of the photothermal dual-curing material according to any one of claims 1 to 7, characterized in that, The thickness of the flat substrate is m - m, and the surface roughness is m - m.

10. A shrinkage rate measurement system for a photo-thermal dual-curing material, characterized in that, The shrinkage rate measurement system includes a test device, a coating device, a flat substrate, a pattern exposure system, a photocuring device, and a thermal curing device; The coating device is used to coat the uncured photo-thermally dual-cured material on the surface of the flat substrate; The pattern exposure system is used to prepare test film squares on the surface of the flat substrate; The test device is used to calculate the volume of the uncured test film square to obtain the volume of the uncured film; The photocuring device is used to perform photocuring treatment on the test film square to obtain a photocured test film square; The test device is further used to calculate the volume of the photocured test film square to obtain the volume of the photocured film; The thermal curing device is used to perform thermal curing treatment on the photocured test film square to obtain a thermally cured test film square; The test device is further used to calculate the volume of the thermally cured test film square to obtain the volume of the thermally cured film; The test device is further used to obtain the target curing shrinkage rate of the photo-thermally dual-cured material based on the volume of the uncured film, the volume of the photocured film, and the volume of the thermally cured film.

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