A multifunctional uv resin and uv hydrolysis adhesive composition containing the same and a method of manufacturing the same

Abstract

The application discloses a multi-functional UV resin, which is synthesized by the reaction of the following resin and monomer, and the molar ratio of the reaction is controlled as monomer C:resin A:monomer B=(3-4):1:(4-4.02), and the structure of the multi-functional UV resin is as follows. The application also discloses a UV hydrolytic adhesive composition, which comprises the multi-functional UV resin, a two-functional high-refractive UV resin, a hydrophilic UV monomer, a hydrophobic UV monomer, a photoinitiator and a wrinkling aid. By adding the synthesized multi-functional UV resin and regulating the proportion of each component in the UV hydrolytic adhesive composition, the problems of slow solidification and deep solidification wrinkling of the UV hydrolytic adhesive in the multi-layer thinning electronic glass are solved, and the problems of difficult balance between the water resistance of the UV hydrolytic adhesive after one-time solidification in hot water and the rapid hydrolysis of the UV hydrolytic adhesive after the deep solidification wrinkling after the one-time solidification are solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of UV glue, in particular to a multi-functional group UV resin, a UV hydrolytic glue composition containing the same and a preparation method thereof. BACKGROUND

[0002] Electronic glass is a high-tech glass product applied in electronic, microelectronic and optoelectronic fields. The current development of technology and application mainly reflects in the display glass and protective cover glass of terminal display products such as mobile phones, tablet computers, liquid crystal televisions and touch screens. With the development of information technology and the upgrading of consumer demand, people's demand for thin and light display terminals is also increasing. Therefore, thinning electronic glass is an important way to achieve the thin and light display terminal products.

[0003] CNC grinding processing is one of the commonly used methods in the electronic glass deep processing industry. However, the thinning electronic glass will cause low processing efficiency and high damage rate when processed in single piece. The laminated bonding processing is to bond multiple layers of thinning electronic glass through UV hydrolytic glue, then uniformly process CNC grinding, then perform UV deep curing and wrinkling, and then remove the UV glue by hydrolysis to make the bonded multiple layers of glass fall off layer by layer to form a single piece.

[0004] However, the current UV hydrolytic glue has the following problems in the laminated bonding of multiple layers of thinning electronic glass:

[0005] 1. The UV hydrolytic glue is slow in curing and deep curing wrinkling in multiple layers of thinning electronic glass, and requires high irradiation energy and long irradiation time;

[0006] 2. The UV hydrolytic glue needs to be resistant to hydrolysis after one-time curing in hot water, and needs to be rapidly hydrolyzed after deep curing and wrinkling again after one-time curing, and the balance point of the two is difficult to control.

[0007] Therefore, it is urgent to provide a new type of UV hydrolytic glue to solve the above problems. SUMMARY

[0008] The technical problem to be solved by the present application is to provide a multi-functional group UV resin, a UV hydrolytic glue composition containing the same and a preparation method thereof. By adding the synthesized multi-functional group UV resin and adjusting the proportion of each component in the UV hydrolytic glue composition, on the one hand, the problem of slow curing and deep curing wrinkling of the UV hydrolytic glue in multiple layers of thinning electronic glass is solved, and on the other hand, the problem that the UV hydrolytic glue needs to be resistant to hydrolysis after one-time curing in hot water and needs to be rapidly hydrolyzed after deep curing and wrinkling again after one-time curing is solved, and the balance of the two is difficult to control.

[0009] To solve the above technical problems, the first technical solution of the present application is to provide a multifunctional UV resin with the following structural formula:

[0010]

[0011] R3 is H or methyl, R4 is H or methyl, and R1 has the following structure:

[0012]

[0013] R2 has the following structure and contains at least H, or all of the following structures:

[0014]

[0015] To solve the above technical problems, the second technical solution of the present application is to provide a preparation method of the multifunctional UV resin as described above, comprising the following steps:

[0016] Step 1: Put resin A into a container and heat to 100℃, then add 25% of the total mass of monomer B and polymerization inhibitor D, and then heat to 109-111℃ again to obtain a first reaction solution; wherein the structure of resin A is as follows:

[0017]

[0018] The structure of monomer B is as follows:

[0019]

[0020] R3 is H or methyl;

[0021] Step 2: Add a catalyst to the first reaction solution and slowly drop the remaining mass of monomer B, control the reaction temperature to be 110-125℃ in this stage, and obtain a second reaction solution;

[0022] Step 3: Heat the second reaction solution to 125-135℃, keep the reaction, take samples to measure the acid value until the acid value is basically unchanged, and obtain a third reaction solution;

[0023] Step 4: Cool the third reaction solution to 60-80℃, add polymerization inhibitor E and monomer C, react for 1-3h, and cool to room temperature to obtain the multifunctional UV resin; wherein the structure of monomer C is as follows:

[0024]

[0025] R4 is H or methyl.

[0026] Chemical reaction equation:

[0027]

[0028] In a preferred embodiment of the present application, the molar ratio of the resin A to the monomer B is 1:(4-4.02).

[0029] In a preferred embodiment of the present application, the polymerization inhibitor D is methylhydroquinone, and the addition amount is 0.05% of the total mass of the resin A and the monomer B.

[0030] In a preferred embodiment of the present application, the polymerization inhibitor E is one of hydroquinone, p-hydroxyanisole, 2-tert-butyl-p-benzosemicarbazide, and 2,5-di-tert-butyl-p-benzosemicarbazide, and the addition amount is 0.2% of the total mass of the resin A and the monomer B.

[0031] In a preferred embodiment of the present application, the catalyst is triphenylphosphine, and the addition amount is 0.25% of the total mass of the resin A and the monomer B.

[0032] In a preferred embodiment of the present application, the molar ratio of the monomer C to the resin A is (3-4):1.

[0033] To solve the above technical problems, a third technical solution of the present application is to provide a UV hydrolytic glue composition, which comprises the multifunctional UV resin as described above and the following components in terms of weight fraction:

[0034]

[0035]

[0036] In a preferred embodiment of the present application, the two-group high-refractive UV resin is selected from one of Youyang Trust-6601 and Youyang Trust-6602; the hydrophilic UV monomer is one of polyethylene glycol (600) dimethyl acrylate (PEG(600)DMA), methoxy polyethylene glycol methacrylate, and ethoxy polyethylene glycol methacrylate; and the hydrophobic UV monomer is at least one of dicyclopentadiene acrylate (DCPA), isobornyl methacrylate (IBOMA), trimethylolpropane triacrylate (TMPTA), dipentaerythritol hexaacrylate (DPHA), and tris(2-hydroxyethyl) isocyanurate triacrylate (THEICTA).

[0037] In a preferred embodiment of the present application, the photoinitiator is at least one of photoinitiator 1173, photoinitiator 651, photoinitiator 819, and photoinitiator ITX; and the wrinkling aid is one of azobisisobutyronitrile (AIBN) and benzoyl peroxide (BPO).

[0038] The present application has the following beneficial effects:

[0039] (1) The present invention provides a multifunctional resin with four highly reactive double bonds at both ends of the molecular chain, which can be rapidly cured under low exposure conditions to obtain a polymer with excellent hydrolysis resistance. In addition, a double bond monomer containing -NCO group is further used to perform a grafting reaction with the secondary hydroxyl group in the resin, thereby increasing the number of double bonds and increasing the functionality of the resin system. On the one hand, it increases the crosslinking density, which further improves its hydrolysis resistance, and on the other hand, it strengthens the curing shrinkage of the resin system and promotes the wrinkling effect.

[0040] (2) The UV hydrolyzable adhesive composition provided by this invention, in addition to the multifunctional UV resin described above, also includes a difunctional high-refractive-index UV resin, a hydrophilic UV monomer, a hydrophobic UV monomer, a photoinitiator, and a wrinkling agent. The difunctional high-refractive-index UV resin used has a refractive index similar to that of glass (1.50), which is beneficial for the effective transmission of UV light during the UV curing process of the well-laminated multilayer thinned electronic glass, reducing light loss and thus facilitating deep curing. During deep curing, the temperature of the sample rapidly rises to above 120°C under high-energy UV light irradiation. At this time, the wrinkling agent contained in the system rapidly decomposes to produce N2 or CO2, which helps wrinkle and reduces the adhesive strength of the film.

[0041] (3) On the one hand, the present invention solves the problem that UV hydrolysate is slow to cure and wrinkle after deep curing in multilayer thinning electronic glass. On the other hand, it solves the problem that UV hydrolysate needs to be resistant to hydrolysis in hot water after one curing and needs to be rapidly hydrolyzed after deep curing and wrinkling after one curing.

[0042] (4) The preparation method provided by the present invention has simple operation process and easy-to-purchase raw materials, and can be used for large-scale production. Detailed Implementation

[0043] The preferred embodiments of the present invention will now be described in detail so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby providing a clearer and more explicit definition of the scope of protection of the present invention.

[0044] The embodiments of the present invention include:

[0045] Example 1:

[0046] A method for preparing a multifunctional UV resin includes the following steps:

[0047] Add 192.10g of resin A to a 1L four-necked flask (or vessel) equipped with a mechanical stirrer, and heat it in an oil bath at 100°C. Once the mechanical stirrer can be turned smoothly by hand, turn it on. Then weigh 146.2g of monomer B (methacrylic acid in this example), controlling the molar ratio of resin A to monomer B (methacrylic acid) to be 1:4. When the temperature inside the four-necked flask (or vessel) reaches 100°C, add 25% of the total mass of monomer B (methacrylic acid), i.e., 36.55g, and 0.17g of methylhydroquinone. Set the oil bath temperature to 110°C. Then, the remaining 109.65 g of monomer B (methacrylic acid) was added to the constant-pressure dropping funnel. When the temperature inside the four-necked flask (or reactor) reached 110°C, 0.85 g of triphenylphosphine was added. The valve of the constant-pressure dropping funnel was then slowly opened, allowing monomer B (methacrylic acid) to slowly drip into the four-necked flask (or reactor). Since this reaction is exothermic, the temperature inside the four-necked flask (or reactor) needed to be controlled at 110-115°C. After monomer B (methacrylic acid) had completely dripped in, the oil bath temperature was set to 125°C. When the temperature inside the four-necked flask (or reactor) reached 125°C, the reaction was maintained at this temperature. A sample was taken to measure the acid value until it was approximately zero, at which point the reaction was considered complete.

[0048] Remove the four-necked flask (or reactor) from the oil bath and allow it to cool naturally in air. Once the temperature inside the flask (or reactor) drops to 80°C, place it in a preheated oil bath at 80°C. Add 0.68 g of 2,5-di-tert-butylhydroquinone and 340.43 g of monomer C (R4 being methyl), maintaining a molar ratio of monomer C (R4 being methyl) to resin A of 3:1. When the temperature inside the four-necked flask (or reactor) reaches 80°C, start timing the reaction for 1 hour. After the reaction is complete, turn off the heating, remove the four-necked flask (or reactor) from the oil bath, and allow it to cool naturally in air to room temperature, yielding the final product, a multifunctional UV resin, abbreviated as Multifunctional UV Resin 1.

[0049] The preparation method of the UV hydrolyzed gel composition in this embodiment is as follows:

[0050] The raw material components, including multifunctional UV resin, difunctional high refractive index UV resin, hydrophilic UV monomer, hydrophobic UV monomer, photoinitiator, and wrinkle-reducing agent, are mixed evenly to obtain a UV hydrolyzed adhesive composition.

[0051] The components of the UV hydrolyzed gels of compositions 1-4 are shown in Table 1.

[0052] Table 1

[0053]

[0054]

[0055] The test samples for each UV hydrolysis composition were prepared using the following methods:

[0056] 1. The UV hydrolyzed adhesive composition is coated onto thinned electronic glass and laminated to a total of 10 pieces of glass;

[0057] 2. The laminated multilayer thinned electronic glass is placed under a UV lamp (18W, effective wavelength 365nm) for initial curing, with an exposure dose of 100mj / cm. 2 Exposure time: 4-8 seconds;

[0058] 3. Place the multi-layer thinned electronic glass after one-time curing in hot water at 90℃ and boil for 3-6 hours;

[0059] 4. The multi-layered thinned electronic glass, after being boiled in water, is exposed to a UV lamp (1000W, effective wavelength 365nm) for deep curing, with an exposure dose of 5000mj / cm. 2 Exposure time: 3-6 minutes;

[0060] 5. Immerse the deeply cured multi-layer thinned electronic glass in hot water at 40-90℃ for no more than 120 seconds to allow the bonded multi-layer glass to detach layer by layer to form a single piece.

[0061] The evaluation criteria and test results for each project are shown in Table 2.

[0062] Table 2

[0063]

[0064]

[0065] Note: ○ indicates compliance with regulations, × indicates non-compliance with regulations.

[0066] In compositions 1-4, the polyfunctional UV resin 1 has 10 double bond functional groups. Table 2 shows that, compared to composition 3, composition 1 has a lower total double bond content, resulting in insufficient crosslinking density. Consequently, after initial curing and boiling at 90°C for 3-6 hours, water seeps into the edges of the laminated glass. After deep curing, the adhesive film is difficult to develop numerous bubble patterns, ultimately leading to hydrolysis (40-90°C / 120s), with only some glass layers detaching. Compared to composition 3, composition 2 has a lower refractive index, reducing effective UV light transmission and affecting initial curing. At 4 seconds of initial curing, the glass layers can still slide; at 8 seconds, although there is no sliding, insufficient internal curing leads to water seepage into the edges of the laminated glass after boiling at 90°C for 3-6 hours. Compared to composition 3, composition 4 lacks a wrinkling aid, thus affecting deep curing wrinkling. When the deep curing time is 3 minutes, there are no large number of air bubbles in the film; when the deep curing time is 6 minutes, although there are a large number of air bubbles in the film, due to the lack of wrinkling agent, hydrolysis (40-90℃ / 120s) eventually results in only some glass layers being able to detach.

[0067] Example 2:

[0068] A method for preparing a multifunctional UV resin includes the following steps:

[0069] Add 192.10g of resin A to a 1L four-necked flask (or vessel) equipped with a mechanical stirrer, and heat it in an oil bath at 100℃. Once the mechanical stirrer can be turned smoothly by hand, turn it on. Then weigh 123.01g of monomer B (acrylic acid in this example), controlling the molar ratio of resin A to monomer B (acrylic acid) to be 1:4.02. When the temperature inside the four-necked flask (or vessel) reaches 100℃, add 25% of the total mass of monomer B (acrylic acid), i.e., 30.75g, and 0.16g of methylhydroquinone. Set the oil bath temperature to 110℃. Then, the remaining 92.26 g of monomer B (acrylic acid) was added to the constant-pressure dropping funnel. When the temperature inside the four-necked flask (or reactor) reached 110°C, 0.79 g of triphenylphosphine was added. The valve of the constant-pressure dropping funnel was then slowly opened, allowing monomer B (acrylic acid) to slowly drip into the four-necked flask (or reactor). Since this reaction is exothermic, the temperature inside the four-necked flask (or reactor) needed to be controlled at 115-120°C. After monomer B (acrylic acid) had completely dripped in, the oil bath temperature was set to 130°C. The reaction was maintained at this temperature, and the acid value was measured until it reached approximately 1.51 mg KOH / g, at which point the reaction was considered complete.

[0070] Remove the four-necked flask (or reactor) from the oil bath and allow it to cool naturally in air. Once the temperature inside the flask (or reactor) drops to 60°C, place it in a preheated oil bath at 60°C. Add 0.63g of p-hydroxyanisole and 406.30g of monomer C (R4 is hydrogen), maintaining a molar ratio of monomer C (R4 is hydrogen) to resin A of 4:1. When the temperature inside the four-necked flask (or reactor) reaches 60°C, start timing the reaction for 3 hours. After the reaction is complete, turn off the heating, remove the four-necked flask (or reactor) from the oil bath, and allow it to cool naturally in air to room temperature to obtain the final product, a multifunctional UV resin, abbreviated as multifunctional UV resin 2.

[0071] The preparation method of the UV hydrolyzed gel composition in this embodiment is the same as that in Example 1, and will not be repeated here.

[0072] The components of the UV hydrolyzed gel of compositions 5-8 are shown in Table 3.

[0073] Table 3

[0074]

[0075] Test samples were prepared for each UV hydrolysis composition using the same method as in Example 1.

[0076] The evaluation criteria and test results for each project are shown in Table 4.

[0077] Table 4

[0078]

[0079] Note: ○ indicates compliance with regulations, × indicates non-compliance with regulations.

[0080] In compositions 5-8, the polyfunctional UV resin 2 has 12 double-bond functional groups. Table 4 shows that, compared to composition 7, composition 5 has a lower total double-bond content, resulting in insufficient crosslinking density. Although composition 5 showed no water penetration at the edges of the laminated glass after boiling in water at 90°C for 3 hours after primary curing, water did penetrate at the edges after boiling at 90°C for 6 hours. Furthermore, after deep curing, the adhesive film was less prone to developing numerous bubble patterns, ultimately leading to hydrolysis (40-90°C / 120s) with only some glass layers detaching. Compared to composition 7, composition 6 has a lower refractive index, reducing effective UV light transmission and affecting primary curing. When cured for 4 seconds, the glass layers could still slide; when cured for 8 seconds, although there was no sliding between the glass layers, insufficient curing within the system resulted in water penetration at the edges of the laminated glass after boiling in water at 90°C for 3-6 hours. Compared to composition 7, composition 8 lacks a wrinkling aid, thus affecting deep curing wrinkling. During deep curing (3-6 minutes), although numerous air bubbles appear in the film, the lack of a wrinkling aid ultimately leads to hydrolysis (40-90℃ / 120s), resulting in only some glass layers detaching.

[0081] Example 3:

[0082] A method for preparing a multifunctional UV resin includes the following steps:

[0083] Add 192.10g of resin A to a 1L four-necked flask (or vessel) equipped with a mechanical stirrer, and heat it in an oil bath at 100℃. Once the mechanical stirrer can be turned smoothly by hand, turn it on. Then weigh 146.57g of monomer B (methacrylic acid in this example), controlling the molar ratio of resin A to monomer B (methacrylic acid) to be 1:4.01. When the temperature inside the four-necked flask (or vessel) reaches 100℃, add 25% of the total mass of monomer B (methacrylic acid), i.e., 36.64g, and 0.17g of methylhydroquinone. Set the oil bath temperature to 110℃. Then, the remaining 109.93 g of monomer B (methacrylic acid) was added to the constant-pressure dropping funnel. When the temperature inside the four-necked flask (or reactor) reached 110°C, 0.85 g of triphenylphosphine was added. The valve of the constant-pressure dropping funnel was then slowly opened, allowing monomer B (methacrylic acid) to slowly drip into the four-necked flask (or reactor). Since this reaction is exothermic, the temperature inside the four-necked flask (or reactor) needed to be controlled at 120-125°C. After monomer B (methacrylic acid) had completely dripped in, the oil bath temperature was set to 135°C. The reaction was maintained at this temperature, and the acid value was measured until it reached approximately 0.7 mg KOH / g, at which point the reaction was considered complete.

[0084] Remove the four-necked flask (or reactor) from the oil bath and allow it to cool naturally in air. Once the temperature inside the flask (or reactor) drops to 70°C, place it in a preheated oil bath at 70°C. Add 0.68 g of 2-tert-butylhydroquinone and 355.51 g of monomer C (R4 is hydrogen), controlling the molar ratio of monomer C (R4 is hydrogen) to resin A to be 3.5:1. When the temperature inside the four-necked flask (or reactor) rises to 70°C, start timing the reaction for 2 hours. After the reaction is complete, turn off the heating, remove the four-necked flask (or reactor) from the oil bath, and allow it to cool naturally in air to room temperature, yielding the final product, a multifunctional UV resin, abbreviated as multifunctional UV resin 3.

[0085] The preparation method of the UV hydrolyzed gel composition in this embodiment is the same as that in Example 1, and will not be repeated here.

[0086] The components of the UV hydrolyzed gel of compositions 9-12 are shown in Table 5.

[0087] Table 5

[0088]

[0089] Test samples were prepared for each UV hydrolysis composition using the same method as in Example 1.

[0090] The evaluation criteria and test results for each project are shown in Table 6.

[0091] Table 6

[0092]

[0093] Note: ○ indicates compliance with regulations, × indicates non-compliance with regulations.

[0094] In compositions 9-12, the polyfunctional UV resin 3 has 11 double bond functional groups. Table 6 shows that, compared to composition 11, composition 9 has a lower total double bond content, resulting in insufficient crosslinking density. Consequently, after initial curing and boiling at 90°C for 3-6 hours, water seeps into the edges of the laminated glass. After deep curing, the adhesive film is difficult to develop numerous bubble patterns, ultimately leading to hydrolysis (40-90°C / 120s), with only some glass layers detaching. Compared to composition 11, composition 10 has a lower refractive index, reducing effective UV light transmission and affecting initial curing. At 4 seconds of initial curing, the glass layers can still slide; at 8 seconds, although there is no sliding, insufficient internal curing leads to water seepage into the edges of the laminated glass after boiling at 90°C for 3-6 hours. Compared to composition 11, composition 12 lacks a wrinkling aid, thus affecting deep curing wrinkling. When the deep curing time is 3 minutes, there are no large number of air bubbles in the film; when the deep curing time is 6 minutes, although there are a large number of air bubbles in the film, due to the lack of wrinkling agent, hydrolysis (40-90℃ / 120s) eventually results in only some glass layers being able to detach.

[0095] Comparative Example 1:

[0096] The preparation method of this comparative example of multifunctional UV resin differs from that of Example 3 in that the molar ratio of resin A to monomer B (methacrylic acid) is 1:3.9. The specific preparation method is as follows:

[0097] Add 192.10g of resin A to a 1L four-necked flask (or vessel) equipped with a mechanical stirrer, and heat it in an oil bath at 100℃. Once the mechanical stirrer can be turned smoothly by hand, turn it on. Then weigh 142.55g of monomer B (methacrylic acid), controlling the molar ratio of resin A to monomer B (methacrylic acid) to be 1:3.9. When the temperature inside the four-necked flask (or vessel) reaches 100℃, add 25% of the total mass of monomer B (methacrylic acid), i.e., 35.64g, and 0.17g of methylhydroquinone. Set the oil bath temperature to 110℃. Then, the remaining 106.91 g of monomer B (methacrylic acid) was added to the constant-pressure dropping funnel. When the temperature inside the four-necked flask (or reactor) reached 110°C, 0.84 g of triphenylphosphine was added. The valve of the constant-pressure dropping funnel was then slowly opened, allowing monomer B (methacrylic acid) to slowly drip into the four-necked flask (or reactor). Since this reaction is exothermic, the temperature inside the four-necked flask (or reactor) needed to be controlled at 120-125°C. After monomer B (methacrylic acid) had completely dripped in, the oil bath temperature was set to 135°C. The reaction was maintained at this temperature, and the acid value was measured until it was approximately zero, at which point the reaction was considered complete.

[0098] Remove the four-necked flask (or reactor) from the oil bath and allow it to cool naturally in air. Once the temperature inside the flask (or reactor) drops to 70°C, place it in a preheated oil bath at 70°C. Add 0.67g of 2-tert-butylhydroquinone and 355.51g of monomer C (R4 is hydrogen), controlling the molar ratio of monomer C (R4 is hydrogen) to resin A to be 3.5:1. When the temperature inside the four-necked flask (or reactor) rises to 70°C, start timing the reaction for 2 hours. After the reaction is complete, turn off the heating, remove the four-necked flask (or reactor) from the oil bath, and allow it to cool naturally in air to room temperature, yielding the final product, a multifunctional UV resin, abbreviated as multifunctional UV resin 4.

[0099] Comparative Example 2:

[0100] The preparation method of this comparative example of multifunctional UV resin differs from that of Example 3 in that the molar ratio of monomer C (R4 is hydrogen) to resin A is 2.5:1. The specific preparation method is as follows:

[0101] Add 192.10g of resin A to a 1L four-necked flask (or vessel) equipped with a mechanical stirrer, and heat in an oil bath at 100℃. Once the mechanical stirrer can be turned smoothly by hand, turn it on. Then weigh 146.57g of monomer B (methacrylic acid), controlling the molar ratio of resin A to monomer B (methacrylic acid) to be 1:4.01. When the temperature inside the four-necked flask (or vessel) reaches 100℃, add 25% of the total mass of monomer B (methacrylic acid), i.e., 36.64g, and 0.17g of methylhydroquinone. Set the oil bath temperature to 110℃. Then, the remaining 109.93 g of monomer B (methacrylic acid) was added to the constant-pressure dropping funnel. When the temperature inside the four-necked flask (or reactor) reached 110°C, 0.85 g of triphenylphosphine was added. The valve of the constant-pressure dropping funnel was then slowly opened, allowing monomer B (methacrylic acid) to slowly drip into the four-necked flask (or reactor). Since this reaction is exothermic, the temperature inside the four-necked flask (or reactor) needed to be controlled at 120-125°C. After monomer B (methacrylic acid) had completely dripped in, the oil bath temperature was set to 135°C. The reaction was maintained at this temperature, and the acid value was measured until it reached approximately 0.7 mg KOH / g, at which point the reaction was considered complete.

[0102] Remove the four-necked flask (or reactor) from the oil bath and allow it to cool naturally in air. Once the temperature inside the flask (or reactor) drops to 70°C, place it in a preheated oil bath at 70°C. Add 0.68 g of 2-tert-butylhydroquinone and 253.94 g of monomer C (R4 is hydrogen), maintaining a molar ratio of monomer C (R4 is hydrogen) to resin A of 2.5:1. When the temperature inside the four-necked flask (or reactor) reaches 70°C, start timing the reaction for 2 hours. After the reaction is complete, turn off the heating, remove the four-necked flask (or reactor) from the oil bath, and allow it to cool naturally in air to room temperature, yielding the final product, a multifunctional UV resin, abbreviated as multifunctional UV resin 5.

[0103] The UV hydrolyzed gel compositions of Comparative Examples 1 and 2 were prepared by the same method as those of the UV hydrolyzed gel composition in Example 3, except that the polyfunctional UV resins used were different, as shown in Table 7.

[0104] Table 7

[0105]

[0106]

[0107] Test samples were prepared for each UV hydrolysis composition using the same method as in Example 1.

[0108] The evaluation criteria and test results for each project are shown in Table 8.

[0109] Table 8

[0110]

[0111] Note: ○ indicates compliance with regulations, × indicates non-compliance with regulations.

[0112] In composition 11, the multifunctional UV resin 3 of Example 3 is used. Since the molar ratio of resin A to monomer B (methacrylic acid) is 1:4.01, the four epoxy groups at both ends of the molecular chain in resin A can completely react to form four double bonds. These four double bonds at both ends of the molecular chain are highly reactive and can be rapidly cured under low exposure conditions, resulting in a polymer with excellent hydrolysis resistance. Furthermore, the molar ratio of monomer C (R4 is hydrogen) to resin A is 3.5:1, and the final number of double-bond functional groups in the multifunctional UV resin 3 is 11. This results in a high crosslinking density, further improving its hydrolysis resistance, and also enhances the curing shrinkage of the resin system, promoting a wrinkling effect. Considering the formulation, all properties of composition 11 meet the requirements.

[0113] In composition 13, the polyfunctional UV resin 4 of Comparative Example 1 is used. Because the molar ratio of resin A to monomer B (methacrylic acid) in polyfunctional UV resin 4 is 1:3.9, the four epoxy groups at both ends of the molecular chain in resin A do not completely react to form four double bonds. Therefore, when curing for 4 seconds, the glass layers can still slide between each other, preventing rapid curing. When curing for 8 seconds, although there is no sliding between the glass layers, the curing process affects the system, leading to water seepage into the edges of the laminated glass after boiling at 90°C for 6 hours. Furthermore, the deep curing speed is also affected. After 3 minutes of deep curing, the film only shows some bubble patterns. After 6 minutes of deep curing, although a large number of bubble patterns appear in the film, only some glass layers can detach during hydrolysis at 40°C. At 90°C, although the glass detaches layer by layer during hydrolysis, residual adhesive remains on the glass.

[0114] In composition 14, the polyfunctional UV resin 5 of Comparative Example 2 is used. Since the molar ratio of monomer C (R4 is hydrogen) to resin A in polyfunctional UV resin 5 is 2.5:1, the number of double bond functional groups in polyfunctional UV resin 5 is 9. As a result, the total double bond content in the system is low, which leads to insufficient crosslinking density of the system. Consequently, the requirements for boiling at 90°C, deep curing and hydrolysis are not met.

[0115] In composition 15, no multifunctional UV resin was added, which ultimately resulted in all properties failing to meet the requirements.

[0116] This embodiment is merely a preferred embodiment of the present invention and is not intended to limit the invention in any other way. Any person skilled in the art may use the above content as inspiration to make changes or modifications to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications listed in the above embodiments that do not depart from the technical essence of the claims of the present invention shall still fall within the scope of protection of the claims of the present invention.

Claims

1. A multifunctional UV resin, characterized in that, The structural formula is as follows: The structure of R1 is as follows: R3 is H or methyl; R2 has the following structure: R4 is H or methyl.

2. A method for preparing the multifunctional UV resin as described in claim 1, characterized in that, Includes the following steps: Step 1: Add resin A to a container and heat to 100°C. First, add 25% of the total mass of monomer B and polymerization inhibitor D, then heat again to 109-111°C to obtain the first reaction solution. The polymerization inhibitor D is methylhydroquinone. The structure of resin A is as follows: The structure of monomer B is as follows: Wherein, R3 is H or methyl; Step 2: Add the catalyst to the first reaction solution, and slowly add the remaining mass of monomer B dropwise. During this stage, control the reaction temperature at 110-125℃ to obtain the second reaction solution; wherein, the catalyst is triphenylphosphine. Step 3: Heat the second reaction solution to 125-135℃, maintain the temperature for reaction, take a sample to measure the acid value until the acid value remains basically unchanged to obtain the third reaction solution; Step 4: Cool the third reaction solution to 60-80℃, add polymerization inhibitor E and monomer C, react for 1-3 hours, and cool to room temperature to obtain the multifunctional UV resin; wherein, the polymerization inhibitor E is one of hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone, and the structure of monomer C is as follows: R4 is H or methyl.

3. The method for preparing the multifunctional UV resin according to claim 2, characterized in that, The molar ratio of resin A to monomer B is 1:(4-4.02).

4. The method for preparing the multifunctional UV resin according to claim 2, characterized in that, The amount of polymerization inhibitor D added is 0.05% of the total mass of resin A and monomer B.

5. The method for preparing the multifunctional UV resin according to claim 2, characterized in that, The amount of polymerization inhibitor E added is 0.2% of the total mass of resin A and monomer B.

6. The method for preparing the multifunctional UV resin according to claim 2, characterized in that, The catalyst is added at a rate of 0.25% of the total mass of resin A and monomer B.

7. The method for preparing the multifunctional UV resin according to claim 2, characterized in that, The molar ratio of monomer C to resin A is (3-4):

1.

8. A UV hydrolyzable adhesive composition, characterized in that, The multifunctional UV resin as described in claim 1 comprises, by weight fraction, the following components: 25-30 parts of multifunctional UV resin 7-12 parts of dual-function high-refractive-index UV resin 10-12 parts of hydrophilic UV monomer 45-50 parts of hydrophobic UV monomer 4-6 parts of photoinitiator Wrinkle-reducing agent 0.5-1 part.

9. The UV hydrolyzed adhesive composition according to claim 8, characterized in that, The bifunctional high refractive index UV resin is selected from one of Youyang Trust-6601 and Youyang Trust-6602; the hydrophilic UV monomer is one of polyethylene glycol (600) dimethacrylate, methoxy polyethylene glycol methacrylate, and ethoxy polyethylene glycol methacrylate; the hydrophobic UV monomer is at least one of dicyclopentadiene acrylate, isobornyl methacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, and tri(2-hydroxyethyl)isocyanurate triacrylate.

10. The UV hydrolyzed gel composition according to claim 8, characterized in that, The photoinitiator is at least one of photoinitiator 1173, photoinitiator 651, photoinitiator 819, and photoinitiator ITX; the wrinkling aid is one of azobisisobutyronitrile and benzoyl peroxide.

Images