Laser deblocking type curing agent and preparation method thereof

Abstract

The invention provides a laser deblocking type curing agent and a preparation method thereof, and relates to the technical field of curing agents, the preparation method comprises the following steps: S1, placing isocyanate in a solvent, and heating and stirring to obtain an isocyanate solution; s2, cooling the isocyanate solution, and dropwise adding a catalyst to obtain a first mixed solution; s3, transferring the first mixed solution into a yellow light area, dropwise adding a sealing agent, and stirring to obtain a second mixed solution; s4, in a protective atmosphere, putting the second mixed solution into an ultrasonic device, starting cold circulation at the same time, and carrying out a closed reaction to obtain a crude product; and S5, filtering the crude product, and purifying the obtained filtrate to obtain the laser deblocking type curing agent. Under the specific irradiation of laser, deblocking can be rapidly carried out, and a curing reaction is initiated, so that a product can be cured within 3 seconds, and various possible adverse effects on a semiconductor precision component in a traditional high-temperature curing process are avoided.

Description

Technical Field

[0001] The present invention relates to the technical field of curing agents, in particular to a laser decapsulating curing agent and a preparation method thereof. Background Art

[0002] Traditional deblocking curing agents rely on a thermal deblocking process, typically requiring heating at 80°C or higher for 20 minutes or longer to ensure the curing agent fully reacts and achieves the desired curing effect. However, in the high-precision, demanding field of semiconductor wafer processing, the situation becomes particularly complex.

[0003] The semiconductor wafer manufacturing process is a precision engineering undertaking requiring extremely precise control. Any slight deviation can irreversibly impact the quality and performance of the entire product. Consequently, many critical processing steps cannot withstand the prolonged heat treatments required by traditional curing agents. Prolonged high-temperature exposure is not only a time-consuming issue; more importantly, it is highly likely to damage the wafer's delicate, nanometer-scale circuit structures, leading to serious consequences such as short circuits and signal distortion. Furthermore, this high-temperature treatment can negatively impact the wafer's overall performance and long-term stability, significantly compromising the reliability of the final product.

[0004] Furthermore, the specialized components integrated on semiconductor wafers, such as state-of-the-art sensors and microprocessors, are extremely sensitive to temperature. These components often need to operate within an extremely precise temperature range to achieve optimal performance. Excessively high temperatures, or drastic temperature fluctuations within a short period of time, can cause changes in the internal structure of these components, leading to performance degradation and, in severe cases, even complete failure of the entire component. Therefore, in the high-precision, demanding field of semiconductor wafer processing, traditional thermal decapsulation curing agents, due to their inherent high-temperature, prolonged heating requirements, are clearly unable to meet all processing requirements.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] The purpose of the present invention is to provide a laser-decapsulating curing agent and a preparation method thereof. Under specific laser irradiation, the agent can be rapidly decapsulated and initiate a curing reaction, so that the product can be cured in just 3 seconds, avoiding the various adverse effects that traditional high-temperature curing processes may have on semiconductor precision components.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions: The present invention provides a method for preparing a laser deblocking curing agent, comprising the following steps: S1: placing isocyanate in a solvent, heating and stirring to obtain an isocyanate solution; S2: Cooling the isocyanate solution and then adding a catalyst dropwise to obtain a first mixed solution; S3: moving the first mixed solution into the yellow light area, adding a blocking agent dropwise, and stirring to obtain a second mixed solution; S4: Under a protective atmosphere, placing the second mixed solution in an ultrasonic device and simultaneously starting a cold cycle to perform a closed reaction to obtain a crude product; S5: filtering the crude product, and purifying the obtained filtrate to obtain a laser deblocking curing agent.

[0008] Further, based on the above technical solution, in step S1, the isocyanate includes one or more of HDI trimer, HDI biuret, HDI uretdione, PDI trimer, and IPDI trimer; And / or, the solvent includes one or more of toluene, isopropyl alcohol, propylene glycol, methyl ether, No. 100 solvent, ethyl acetate, and butyl acetate; And / or, in step S1, the heating and stirring includes: a temperature of 45-55° C. and a stirring time of 30-60 min.

[0009] Furthermore, based on the above technical solution, in step S1, the solid content of the isocyanate solution is 40-60 wt%.

[0010] Furthermore, based on the above technical solution, in step S2, the catalyst is an active amine catalyst; The active amine catalyst includes one or more of triethylenediamine and triethylenediamine; And / or, in step S2, the cooling refers to cooling to ≤30°C; And / or, in step S2, the dropping rate is 0.5-1 drop / min; And / or, in step S2, the mass ratio of the catalyst to the isocyanate in the isocyanate solution is (0.0005-0.001):1.

[0011] Furthermore, based on the above technical solution, in step S3, the yellow light region refers to light with a wavelength of 570-600nm; And / or, in step S3, the blocking agent includes one or more of 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone; And / or, in step S3, the dropping rate is 0.5-1 drop / min; And / or, in step S3, the mass ratio of the blocking agent to the isocyanate in the isocyanate solution is (1-3):1.

[0012] Furthermore, based on the above technical solution, in step S4, the protective atmosphere includes one or more of nitrogen, argon, and helium; And / or, in step S4, the frequency of the ultrasonic device is greater than 20000 Hz; and / or, in step S4, the temperature of the cold cycle is ≤35°C; And / or, in step S4, the blocking reaction time is 7-9 hours.

[0013] Furthermore, based on the above technical solution, in step S5, the purification is performed by low-temperature rotary evaporation.

[0014] The present invention also provides a laser deblocking curing agent prepared by the above-mentioned preparation method of the laser deblocking curing agent.

[0015] Furthermore, based on the above technical solution, the laser deblocking curing agent can be cured within 3 seconds or less under laser irradiation.

[0016] Furthermore, based on the above technical solution, the power of the laser is 100mW-100W, and the wavelength is 355-405nm.

[0017] The present invention provides a laser deblocking curing agent and a preparation method thereof, which have the following beneficial effects: 1. The laser decapsulation curing agent provided by the present invention can quickly decapsulate and trigger a curing reaction under specific laser irradiation, so that the product can be cured in just 3 seconds. This huge improvement in speed not only greatly shortens the production cycle, but more importantly, it also avoids the various adverse effects that the traditional high-temperature curing process may have on semiconductor precision components. In the semiconductor manufacturing process, the use of the laser decapsulation curing agent provided by the present invention can significantly reduce the thermal shock of temperature on the device, reduce material deformation and internal stress caused by temperature changes, and thus protect the integrity and performance of the device. At the same time, since laser irradiation is highly localized and controllable, the curing area can be precisely controlled to avoid thermal effects on the surrounding non-curing areas, further improving the manufacturing precision and yield of semiconductor devices.

[0018] 2. The catalyst selected in the blocking reaction of the present invention is an active amine catalyst, which can not only effectively promote the reaction between the isocyanate and the blocking agent, increase the reaction rate, and thus accelerate the preparation process of the curing agent; it also helps to adjust the molecular structure and chemical properties of the curing agent, so that it can be unblocked more quickly under laser irradiation, thereby achieving an efficient curing reaction.

[0019] 3. The present invention restricts the reaction to the yellow light region to prevent certain light-sensitive substances from undergoing unnecessary photochemical reactions under ordinary light, thereby affecting the reaction and product quality. During the preparation of laser-deblocking curing agents, some components sensitive to visible light may undergo photodecomposition, polymerization, or other side reactions under ordinary light, leading to decreased reaction selectivity, reduced yield, and unstable product performance. Yellow light, however, has a longer wavelength and relatively lower energy, which has less impact on these light-sensitive substances. Conducting the reaction in the yellow light region minimizes light interference with the reaction, ensuring smooth reaction progress and improving product purity and quality. DETAILED DESCRIPTION

[0020] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention. The process parameters for which specific conditions are not specified in the following examples are generally in accordance with conventional conditions.

[0021] The endpoints of the ranges and any values disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values can be combined with each other to form one or more new numerical ranges, and these numerical ranges should be considered to be specifically disclosed in the present invention.

[0022] According to a first aspect of the present invention, there is provided a method for preparing a laser deblocking curing agent, comprising the following steps: S1: placing isocyanate in a solvent, heating and stirring to obtain an isocyanate solution; S2: Cooling the isocyanate solution and then adding a catalyst dropwise to obtain a first mixed solution; S3: moving the first mixed solution into the yellow light area, adding a blocking agent dropwise, and stirring to obtain a second mixed solution; S4: Under a protective atmosphere, placing the second mixed solution in an ultrasonic device and simultaneously starting a cold cycle to perform a closed reaction to obtain a crude product; S5: filtering the crude product, and purifying the obtained filtrate to obtain a laser deblocking curing agent.

[0023] Specifically, the laser decapsulation curing agent provided by the present invention can quickly decapsulate and initiate a curing reaction under specific laser irradiation, so that the product can be cured in just 3 seconds. This huge improvement in speed not only greatly shortens the production cycle, but more importantly, it also avoids the various adverse effects that the traditional high-temperature curing process may have on semiconductor precision components. In the semiconductor manufacturing process, the use of the laser decapsulation curing agent provided by the present invention can significantly reduce the thermal shock of temperature on the device, reduce material deformation and internal stress caused by temperature changes, and thus protect the integrity and performance of the device. At the same time, since laser irradiation is highly localized and controllable, the curing area can be precisely controlled to avoid thermal effects on the surrounding non-curing areas, further improving the manufacturing precision and yield of semiconductor devices.

[0024] As an optional embodiment of the present invention, in step S1, the isocyanate includes one or more of HDI trimer, HDI biuret, HDI uretdione, PDI trimer, and IPDI trimer; The solvent includes one or more of toluene, isopropyl alcohol, propylene glycol, methyl ether, No. 100 solvent, ethyl acetate, and butyl acetate; In step S1, the heating and stirring include: a temperature of 45-55°C (such as 48°C, 50°C, 52°C, 54°C, etc.), and a stirring time of 30-60min (such as 35min, 40min, 45min, 50min, 55min, etc.).

[0025] As an optional embodiment of the present invention, in step S1, the solid content of the isocyanate solution is 40-60 wt%.

[0026] Specifically, the present invention limits the solid content of the isocyanate solution to 40-60 wt% in order to balance the reaction rate, the solubility of the product and the convenience of subsequent processing; too low a solid content may lead to a slow reaction rate, while too high a solid content may increase the viscosity of the solution, which is not conducive to subsequent operations.

[0027] As an optional embodiment of the present invention, in step S2, the catalyst is an active amine catalyst; Preferably, the active amine catalyst includes one or more of triethylenediamine (TEDA) and triethylenediamine (TDEA); Specifically, the purpose of selecting the active amine catalyst in the present invention is: (1) Improve reaction activity: Active amine catalysts can effectively promote the reaction between isocyanate and blocking agent, increase the reaction rate, and thus accelerate the preparation process of curing agent; (2) Lowering the reaction temperature: Active amine catalysts may have better catalytic activity and can promote the reaction at relatively low temperatures, which helps to reduce energy consumption and reduce side reactions during the reaction; (3) Optimizing the unblocking performance: The selection of active amine catalysts may help adjust the molecular structure and chemical properties of the curing agent, so that it can be unblocked more quickly under laser irradiation and achieve an efficient curing reaction; (4) Adaptation to laser curing process: Laser deblocking curing agents need to be quickly deblocked and initiate curing reaction under laser irradiation. The use of active amine catalysts may help the curing agent better adapt to this special curing process requirement.

[0028] In step S2, the cooling refers to cooling to ≤30°C; Specifically, the present invention slowly cools the isocyanate solution to ≤30°C for the following purposes: (1) Control the reaction rate and slow down the reaction between isocyanate and the subsequently added catalyst and blocking agent, making the reaction more controllable and reducing the possibility of side reactions and product quality degradation; (2) Improve the reaction selectivity, making the reaction more inclined to produce the target product and reduce the formation of by-products; (3) Protect the stability of reactants and products, prevent isocyanate from decomposing or undergoing other adverse chemical reactions at higher temperatures, and maintain the stability of the generated intermediates and final products; (4) Avoid premature activation of the catalyst due to excessively high temperature, ensure the controllability of the reaction, improve the selectivity and yield of the reaction, and ensure the performance and quality of the curing agent.

[0029] In step S2, the dropping rate is 0.5-1 drop / min; In step S2, the mass ratio of the catalyst to the isocyanate in the isocyanate solution is (0.0005-0.001):1, such as 0.0006:1, 0.0007:1, 0.0008:1, or 0.0009:1.

[0030] Specifically, the present invention limits the mass ratio of the catalyst to the isocyanate in the isocyanate solution to (0.0005-0.001):1. The catalyst within this ratio range can provide sufficient catalytic activity to promote the effective reaction between the isocyanate and the blocking agent, ensuring that the preparation of the curing agent can be successfully completed; and the appropriate mass ratio can ensure a moderate reaction rate; if the mass ratio of the catalyst is too low, the catalytic effect of the catalyst is insufficient, the reaction rate is too slow, and the production cycle will be extended; and if the mass ratio of the catalyst is too high, the reaction may be too violent, increase the probability of side reactions, and affect product quality.

[0031] As an optional embodiment of the present invention, in step S3, the yellow light region refers to light with a wavelength of 570-600 nm; Specifically, the present invention limits the reaction to the yellow light region to prevent certain light-sensitive substances from undergoing unnecessary photochemical reactions under ordinary light, thereby affecting the progress of the reaction and the quality of the product. During the preparation of laser-deblocking curing agents, some components are sensitive to visible light. Under ordinary light, these substances may undergo photodecomposition, polymerization, or other side reactions, resulting in decreased reaction selectivity, reduced yield, and unstable product performance. Yellow light, however, has a longer wavelength and relatively lower energy, and has less impact on these light-sensitive substances. Conducting the reaction in the yellow light region can minimize light interference with the reaction, ensure the smooth progress of the reaction, and improve the purity and quality of the product.

[0032] In step S3, the blocking agent includes one or more of 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone; Specifically, the molecular structure of the above-mentioned blocking agent contains groups that are sensitive to laser energy, such as carbonyl (C=O) and benzene ring. Under the yellow light region, the influence of other light on the groups sensitive to laser energy is avoided, ensuring the selectivity of the blocking agent for isocyanate active groups, thereby ensuring the purity of the product.

[0033] Furthermore, during the blocking reaction, the active groups of the isocyanate, in the presence of an active amine catalyst, generate a light-sensitive intermediate product. Yellow light inhibits the activity of this intermediate product, allowing it to react with the blocking agent, blocking the active isocyanate groups. When irradiated with laser light, the laser energy breaks the chemical bond between the blocking agent and the isocyanate, unblocking the isocyanate and releasing the active isocyanate groups, thereby initiating the curing reaction.

[0034] In step S3, the dropping rate is 0.5-1 drop / min; In step S3, the mass ratio of the blocking agent to the isocyanate in the isocyanate solution is (1-3):1, such as 1.2:1, 1.5:1, 1.7:1, 2:1, 2.2:1, 2.5:1, 2.7:1, etc.; Specifically, the present invention limits the mass ratio of the blocking agent to the isocyanate in the isocyanate solution to (1-3):1, in order to ensure that the blocking agent can fully and efficiently react with the isocyanate, thereby blocking as many isocyanate reactive groups as possible; when the ratio of the blocking agent is lower than the lower limit of the above-mentioned limited range, it may not be possible to fully block all the isocyanate reactive groups, which will result in residual unblocked isocyanate groups in the product, which may affect the stability and reactivity of the product; on the contrary, if the ratio of the blocking agent is higher than the upper limit of the above-mentioned limited range, it may lead to excessive blocking, which will not only increase costs, but also may introduce unnecessary impurities, affecting the purity and performance of the product.

[0035] In step S3, the stirring refers to stirring the second mixed solution until it is uniform.

[0036] As an optional embodiment of the present invention, in step S4, the protective atmosphere includes one or more of nitrogen, argon, and helium; In step S4, the frequency of the ultrasonic device is greater than 20000 Hz; In step S4, the temperature of the cold cycle is ≤35°C; Specifically, during the blocking reaction, by limiting the cold cycle temperature to ≤35°C, on the one hand, appropriate low temperature conditions can effectively slow down the reaction rate, making the reaction between the blocking agent and the isocyanate proceed more smoothly and orderly; on the other hand, it is to prevent the reactants and products from thermally degrading due to excessive temperature, resulting in changes in chemical structure and properties, and thus affecting the stability and application value of the product; in addition, controlling the cold cycle temperature to ≤35°C also helps to optimize the performance of the curing agent. In the subsequent laser unsealing process, the curing agent needs to be able to quickly and effectively achieve unsealing and curing reactions. Appropriate low temperature conditions can improve the storage stability and reactivity of the curing agent, allowing it to reach the required reaction conditions more quickly during the unsealing process, thereby improving the practical value and application effect of the curing agent.

[0037] In step S4, the blocking reaction time is 7-9 hours.

[0038] As an optional embodiment of the present invention, in step S5, the purification is low-temperature rotary evaporation, which can effectively remove impurities and solvent residues in the sample, thereby improving the purity of the sample.

[0039] According to a second aspect of the present invention, a laser deblocking curing agent prepared by the above-mentioned preparation method of the laser deblocking curing agent is provided.

[0040] As an optional embodiment of the present invention, the laser deblocking curing agent can be cured within 3 seconds or less under laser irradiation.

[0041] As an optional embodiment of the present invention, the power of the laser is 100mW-100W, and the wavelength is 355-405nm.

[0042] The present invention will be further described in detail below with reference to specific examples and comparative examples.

[0043] Example 1

[0044] S1: HDI trimer was placed in toluene and heated with stirring at 50°C for 30 min to obtain an isocyanate solution; Wherein, the solid content of the isocyanate solution is 50wt%; S2: Cooling the isocyanate solution to ≤30° C., and then adding a catalyst, triethylenediamine, dropwise to obtain a first mixed solution; The catalyst was added at a rate of 0.5 drops / min. The mass ratio of the catalyst to the isocyanate in the isocyanate solution is 0.0005:1; S3: moving the first mixed solution to the yellow light region, adding 1-hydroxycyclohexyl phenyl ketone dropwise, and stirring to obtain a second mixed solution; Among them, the dropping rate is 0.5 drops / min; The mass ratio of the blocking agent to the isocyanate in the isocyanate solution is 1:1; S4: Under a nitrogen atmosphere, placing the second mixed solution in an ultrasonic device and simultaneously starting a cooling cycle to keep the reaction temperature ≤35°C for a closed reaction of 7-9 hours to obtain a crude product; S5: filtering the crude product, and then purifying the obtained filtrate by low-temperature rotary evaporation to obtain a laser deblocking curing agent.

[0045] The curing agent prepared in this example was mixed with a resin model SG-U0640 (manufactured by Guangzhou Haoyi New Materials Technology Co., Ltd.) in a mass ratio of 10:1. The mixture was irradiated with a laser having a power of 50 W and a wavelength of 400 nm, and cured in 2.5 seconds. The hardness of the cured film layer was tested to be 1H according to GB / T6739-2006. After wiping with alcohol 50 times, the surface of the cured film remained intact.

[0046] Example 2

[0047] S1: isocyanate HDI biuret is placed in isopropyl alcohol, heated and stirred at 55°C for 40 minutes to obtain an isocyanate solution; Wherein, the solid content of the isocyanate solution is 60wt%; S2: Cooling the isocyanate solution to ≤30° C., and then adding a catalyst, triethylenediamine, dropwise to obtain a first mixed solution; The catalyst was added at a rate of 0.5 drops / min. The mass ratio of the catalyst to the isocyanate in the isocyanate solution is 0.0008:1; S3: moving the first mixed solution to the yellow light region, adding a blocking agent 2-hydroxy-2-methyl-1-phenyl-1-propanone dropwise, and stirring to obtain a second mixed solution; Among them, the dropping rate is 0.5 drops / min; The mass ratio of the blocking agent to the isocyanate in the isocyanate solution is 1.5:1; S4: Under an argon atmosphere, placing the second mixed solution in an ultrasonic device and simultaneously starting a cooling cycle to keep the reaction temperature ≤35° C., and conducting a closed reaction for 9 hours to obtain a crude product; S5: filtering the crude product, and then purifying the obtained filtrate by low-temperature rotary evaporation to obtain a laser deblocking curing agent.

[0048] The curing agent prepared in this example was mixed with a resin model SG-U0640 (manufactured by Guangzhou Haoyi New Materials Technology Co., Ltd.) in a mass ratio of 10:1. The mixture was irradiated with a laser having a power of 50 W and a wavelength of 400 nm and cured in 3 seconds. The hardness of the cured film layer was tested to be 1H according to GB / T6739-2006. After wiping with alcohol 50 times, the surface of the cured film remained intact.

[0049] Example 3

[0050] S1: isocyanate HDI uretdione is placed in solvent propylene glycol, heated and stirred at 50°C for 30 minutes to obtain an isocyanate solution; Wherein, the solid content of the isocyanate solution is 40wt%; S2: Cooling the isocyanate solution to ≤30° C., and then adding a catalyst, triethylenediamine, dropwise to obtain a first mixed solution; The catalyst was added at a rate of 0.5 drops / min. The mass ratio of the catalyst to the isocyanate in the isocyanate solution is 0.0007:1; S3: moving the first mixed solution to the yellow light region, adding a blocking agent 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone dropwise, and stirring to obtain a second mixed solution; Among them, the dropping rate is 0.5 drops / min; The mass ratio of the blocking agent to the isocyanate in the isocyanate solution is 2:1; S4: Under a nitrogen atmosphere, placing the second mixed solution in an ultrasonic device and simultaneously starting a cooling cycle to keep the reaction temperature ≤35° C., and conducting a closed reaction for 9 hours to obtain a crude product; S5: filtering the crude product, and then purifying the obtained filtrate by low-temperature rotary evaporation to obtain a laser deblocking curing agent.

[0051] The curing agent prepared in this example was mixed with a resin model SG-U0640 (manufactured by Guangzhou Haoyi New Materials Technology Co., Ltd.) at a mass ratio of 10:1. The mixture was irradiated with a laser having a power of 50 W and a wavelength of 400 nm for 2 seconds to achieve curing. The hardness of the cured film layer was tested to be 1H according to GB / T6739-2006. After wiping with alcohol 50 times, the surface of the cured film remained intact.

[0052] Example 4

[0053] S1: isocyanate PDI trimer is placed in ethyl acetate solvent, heated and stirred at 50°C for 30 minutes to obtain an isocyanate solution; Wherein, the solid content of the isocyanate solution is 50wt%; S2: Cooling the isocyanate solution to ≤30° C., and then adding a catalyst, triethylenediamine, dropwise to obtain a first mixed solution; The catalyst was added at a rate of 0.5 drops / min. The mass ratio of the catalyst to the isocyanate in the isocyanate solution is 0.001:1; S3: moving the first mixed solution into the yellow light region, adding a blocking agent, 1-hydroxycyclohexyl phenyl ketone, and stirring to obtain a second mixed solution; Among them, the dropping rate is 0.5 drops / min; The mass ratio of the blocking agent to the isocyanate in the isocyanate solution is 1:1; S4: Under a nitrogen atmosphere, placing the second mixed solution in an ultrasonic device and simultaneously starting a cooling cycle to keep the reaction temperature ≤35° C., and conducting a closed reaction for 8 hours to obtain a crude product; S5: filtering the crude product, and then purifying the obtained filtrate by low-temperature rotary evaporation to obtain a laser deblocking curing agent.

[0054] The curing agent prepared in this example was mixed with a resin model SG-U0640 (manufactured by Guangzhou Haoyi New Materials Technology Co., Ltd.) in a mass ratio of 10:1. The mixture was irradiated with a laser having a power of 50 W and a wavelength of 400 nm and cured in 3 seconds. The hardness of the cured film layer was tested to be 1H according to GB / T6739-2006. After wiping with alcohol 50 times, the surface of the cured film remained intact.

[0055] Example 5

[0056] S1: placing isocyanate IPDI trimer in solvent methyl ether, heating and stirring at 55°C for 40 minutes to obtain an isocyanate solution; Wherein, the solid content of the isocyanate solution is 50wt%; S2: Cooling the isocyanate solution to ≤30° C., and then adding a catalyst, triethylenediamine, dropwise to obtain a first mixed solution; The catalyst was added at a rate of 0.5 drops / min. The mass ratio of the catalyst to the isocyanate in the isocyanate solution is 0.0005:1; S3: moving the first mixed solution into the yellow light region, adding a blocking agent 2-hydroxy-2-methyl-1-phenyl-1-propanone dropwise, and stirring to obtain a second mixed solution; Among them, the dropping rate is 0.5 drops / min; The mass ratio of the blocking agent to the isocyanate in the isocyanate solution is 1:1; S4: Under a nitrogen atmosphere, placing the second mixed solution in an ultrasonic device and simultaneously starting a cooling cycle to keep the reaction temperature ≤35° C., and conducting a closed reaction for 9 hours to obtain a crude product; S5: filtering the crude product, and then purifying the obtained filtrate by low-temperature rotary evaporation to obtain a laser deblocking curing agent.

[0057] The curing agent prepared in this example was mixed with a resin model SG-U0640 (manufactured by Guangzhou Haoyi New Materials Technology Co., Ltd.) in a mass ratio of 10:1. The mixture was irradiated with a laser having a power of 50 W and a wavelength of 400 nm and cured in 3 seconds. The hardness of the cured film layer was tested to be 1H according to GB / T6739-2006. After wiping with alcohol 50 times, the surface of the cured film remained intact.

[0058] Comparative Example 1 The difference between this comparative example and Example 1 is that the catalyst added in step S2 is an organic tin catalyst dibutyltin dilaurate, and the remaining steps and technical parameters are the same as those in Example 1.

[0059] The curing agent prepared in this comparative example was mixed with a resin model SG-U0640 (manufactured by Guangzhou Haoyi New Materials Technology Co., Ltd.) at a mass ratio of 10:1 and irradiated with a laser with a wavelength of 400 nm. No curing occurred within 3 seconds, and subsequent tests such as hardness could not be performed.

[0060] This is because dibutyltin dilaurate is an organic tin catalyst, and its catalytic mechanism is different from that of active amine catalysts. In the presence of organic tin catalysts, no light-sensitive active intermediates are produced. Therefore, under laser irradiation, the curing speed slows down and curing cannot be completed within just 3 seconds.

[0061] Comparative Example 2 The difference between this comparative example and Example 1 is that in step S3, the reaction is not carried out in the yellow light zone, but under normal natural light conditions. The remaining steps and technical parameters are the same as those in Example 1.

[0062] The curing agent prepared in this comparative example was mixed with a resin model SG-U0640 (manufactured by Guangzhou Haoyi New Materials Technology Co., Ltd.) at a mass ratio of 10:1 and irradiated with a laser with a wavelength of 400 nm. No curing occurred within 3 seconds, and subsequent tests such as hardness could not be performed.

[0063] This is because Comparative Example 2 did not react under the conditions of the yellow light region, and the active amine catalyst and the intermediate active product produced were decomposed by light, resulting in reduced activity or even complete inactivation. Therefore, no curing occurred when laser irradiation was used.

[0064] Finally, it should be noted that the above 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 above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a laser deblocking curing agent, characterized in that: The steps include: S1: placing isocyanate in a solvent, heating and stirring to obtain an isocyanate solution; S2: Cooling the isocyanate solution and then adding a catalyst dropwise to obtain a first mixed solution; S3: moving the first mixed solution into the yellow light area, adding a blocking agent dropwise, and stirring to obtain a second mixed solution; S4: Under a protective atmosphere, placing the second mixed solution in an ultrasonic device and simultaneously starting a cold cycle to perform a closed reaction to obtain a crude product; S5: filtering the crude product, and purifying the obtained filtrate to obtain a laser deblocking curing agent.

2. The method for preparing the laser deblocking curing agent according to claim 1, characterized in that: In step S1, the isocyanate includes one or more of HDI trimer, HDI biuret, HDI uretdione, PDI trimer, and IPDI trimer; And / or, the solvent includes one or more of toluene, isopropyl alcohol, propylene glycol, methyl ether, No. 100 solvent, ethyl acetate, and butyl acetate; And / or, in step S1, the heating and stirring includes: a temperature of 45-55° C. and a stirring time of 30-60 min.

3. The method for preparing the laser deblocking curing agent according to claim 1, characterized in that: In step S1, the solid content of the isocyanate solution is 40-60 wt%.

4. The method for preparing the laser deblocking curing agent according to claim 1, characterized in that: In step S2, the catalyst is an active amine catalyst; The active amine catalyst includes one or more of triethylenediamine and triethylenediamine; And / or, in step S2, the cooling refers to cooling to ≤30°C; And / or, in step S2, the dropping rate is 0.5-1 drop / min; And / or, in step S2, the mass ratio of the catalyst to the isocyanate in the isocyanate solution is (0.0005-0.001):

1.

5. The method for preparing the laser deblocking curing agent according to claim 1, characterized in that: In step S3, the yellow light region refers to light with a wavelength of 570-600 nm; And / or, in step S3, the blocking agent includes one or more of 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone; And / or, in step S3, the dropping rate is 0.5-1 drop / min; And / or, in step S3, the mass ratio of the blocking agent to the isocyanate in the isocyanate solution is (1-3):

1.

6. The method for preparing the laser deblocking curing agent according to claim 1, characterized in that: In step S4, the protective atmosphere includes one or more of nitrogen, argon, and helium; And / or, in step S4, the frequency of the ultrasonic device is greater than 20000 Hz; and / or, in step S4, the temperature of the cold cycle is ≤35°C; And / or, in step S4, the blocking reaction time is 7-9 hours.

7. The method for preparing a laser deblocking curing agent according to claim 1, characterized in that: In step S5, the purification is performed by low-temperature rotary evaporation.

8. A laser deblocking curing agent prepared by the method for preparing a laser deblocking curing agent according to any one of claims 1 to 7.

9. The laser deblocking curing agent according to claim 8, characterized in that: The laser deblocking curing agent can be cured within 3 seconds or less under laser irradiation.

10. The laser deblocking curing agent according to claim 9, characterized in that: The power of the laser is 100mW-100W, and the wavelength is 355-405nm.