High-sealability photo-thermal dual-curing frame sealing glue and preparation method thereof

Abstract

The invention belongs to the technical field of adhesives, and particularly relates to a high-sealability photo-thermal dual-curing frame sealing adhesive, which is prepared from the following raw materials in parts by weight: 60 to 100 parts of bisphenol A epoxy resin, 10 to 30 parts of organic silicon modified polyurethane acrylate, 10 to 20 parts of filler, 5 to 10 parts of zinc-containing compound, 0.1 to 2 parts of curing agent, 1 to 6 parts of photoinitiator, 1 to 5 parts of silane coupling agent and 15 to 30 parts of organic solvent. The organic silicon modified polyurethane acrylate is prepared by the following steps: firstly, reacting double-end hydroxypropyl silicone oil, 2, 6-piperazine diethanol, dimethyl glyoxime and hexamethylene diisocyanate to form a prepolymer, and then reacting the prepolymer with pentaerythritol triacrylate; the obtained frame sealing glue can still keep excellent bonding performance in a high-temperature and high-humidity environment, the sealing performance is greatly enhanced, liquid crystals are well prevented from being polluted, and the yield of liquid crystal display products is increased.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of adhesives, and particularly relates to a high-sealing photothermal dual-curing frame sealing adhesive and a preparation method thereof. BACKGROUND

[0002] In the field of modern display technology, liquid crystal display devices have the advantages of high definition, low power consumption, thinness, etc., and have been widely applied to many fields such as smart phones, tablet computers, notebook computers, televisions, vehicle-mounted displays, and various industrial control terminals, becoming one of the current mainstream display technologies. In the manufacturing process of the liquid crystal display device, the liquid crystal frame sealing adhesive, as a core key material, mainly functions to effectively bond the upper and lower two glass substrates in the liquid crystal display panel, and at the same time, to build a sealed space to prevent the leakage of liquid crystal in the box, and to block the invasion of external moisture, oxygen, dust and other impurities into the panel, thereby ensuring the normal working performance and long-term reliability of the liquid crystal display device.

[0003] The liquid crystal display device is easily disturbed by the external environment during use. Under the action of temperature cycling, the thermal stress generated by the difference in the thermal expansion coefficient between the frame sealing adhesive and the glass substrate will be repeatedly accumulated, which can easily lead to interface peeling or cracking of the adhesive layer. In a high-humidity environment, if the sealing property of the frame sealing adhesive is poor, external moisture will gradually penetrate into the panel and react with the liquid crystal material, causing the liquid crystal to deteriorate, display to appear residual images or bright spots, and also corroding the electrode layer and the driving circuit, affecting the electrical performance and service life of the device.

[0004] Therefore, the consequences caused by the poor sealing property of the frame sealing adhesive are extremely serious. Not only will it cause problems such as display defects and electrical performance degradation of the liquid crystal display device, greatly reducing the yield and use reliability of the product, but also will shorten the service life of the device, increase the after-sales maintenance cost, and have an adverse effect on the product quality and market competitiveness of the liquid crystal display industry.

[0005] Based on the above statements, the application provides a high-sealing photothermal dual-curing frame sealing adhesive and a preparation method thereof. SUMMARY

[0006] The application aims to provide a high-sealing photothermal dual-curing frame sealing adhesive and a preparation method thereof, to solve the problem of poor sealing property of the frame sealing adhesive.

[0007] In the first aspect, the application provides a high-sealing photothermal dual-curing frame sealing adhesive, which adopts the following technical scheme: A high sealing light-thermal double curing frame sealant, comprising the following raw materials by weight: bisphenol A type epoxy resin 60-100 parts, organic silicon modified polyurethane acrylate 10-30 parts, filler 10-20 parts, zinc-containing compound 5-10 parts, curing agent 0.1-2 parts, photoinitiator 1-6 parts, silane coupling agent 1-5 parts, organic solvent 15-30 parts; The organic silicon modified polyurethane acrylate is obtained by first reacting di-end hydroxypropyl silicone oil, 2,6-piperazine diethanol, dimethyl ethanedione and hexamethylene diisocyanate to form a prepolymer, and then reacting the prepolymer with pentaerythritol triacrylate.

[0008] Preferably, the preparation method of the organic silicon modified polyurethane acrylate is as follows: The di-end hydroxypropyl silicone oil, 2,6-piperazine diethanol, dimethyl ethanedione, organic tin are added into acetone, and after dehydration under reduced pressure, hexamethylene diisocyanate is added dropwise through a constant pressure dropping funnel under stirring, and the dropping is completed within 1 h, and the reaction is carried out under reflux at 60-70℃ for 2-3 h to obtain a prepolymer; then pentaerythritol triacrylate and a polymerization inhibitor are added into the prepolymer, and the temperature is raised to 75-85℃, and the reaction is carried out under reflux for 3-6 h, and then the temperature is cooled to room temperature to discharge the product to obtain the organic silicon modified polyurethane acrylate.

[0009] Preferably, the mass ratio of the di-end hydroxypropyl silicone oil, 2,6-piperazine diethanol, dimethyl ethanedione, hexamethylene diisocyanate, pentaerythritol triacrylate, organic tin, polymerization inhibitor, acetone is 100:(17-35):(2.3-6.9):(45-80):(40-75):(0.2-1.0):(0.2-0.6):(80-150).

[0010] Preferably, the molecular weight of the di-end hydroxypropyl silicone oil is 500-2000, and the hydroxyl content is 1.5wt%-5wt%.

[0011] Preferably, the organic tin is one or more of stannous octoate, dibutyltin dilaurate, dioctyltin dilaurate and dibutyltin acetate.

[0012] Preferably, the polymerization inhibitor is one or more of p-hydroxyanisole, acryloyl morpholine and phenothiazine.

[0013] Preferably, the filler is one or more of talc, kaolin, magnesium hydroxide, silicon dioxide, calcium carbonate and calcium silicate.

[0014] Preferably, the zinc-containing compound is one or more of zinc chloride, zinc sulfate, zinc stearate, zinc acetate, zinc triflate and zinc acetylacetonate.

[0015] Preferably, the curing agent is one or more of aniline, methoxyaniline, N,N'-dimethylethylenediamine, ethanolamine, 4,4'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl ether.

[0016] Preferably, the photoinitiator is one or more of 2,4,6-trimethylbenzoylphenyl ethyl phosphinate, 4-acryloyloxybenzophenone, 4-dimethylamino-benzoic acid ethyl ester, benzophenone.

[0017] Preferably, the silane coupling agent is methacryloyloxypropyltrimethoxysilane and / or 3-glycidyloxypropyltrimethoxysilane.

[0018] Preferably, the organic solvent is one or more of isopropyl alcohol, toluene, acetone, N,N-dimethylformamide, ethyl acetate.

[0019] In a second aspect, the present application provides a preparation method of a high-sealing light-thermal dual-curing frame sealant, which adopts the following technical scheme: A preparation method of a high-sealing light-thermal dual-curing frame sealant, comprising the following steps: S1, mixing bisphenol A type epoxy resin and silicone modified polyurethane acrylate, stirring uniformly to obtain mixture one; S2, adding fillers, zinc-containing compounds and silane coupling agents into an organic solvent, stirring uniformly, cooling to room temperature to obtain mixture two; S3, adding mixture two into mixture one, mixing uniformly, adding a photoinitiator and a curing agent, stirring uniformly to obtain mixture three; S4, grinding mixture three, filtering, defoaming, light-shielding storage to obtain the frame sealant.

[0020] The present application has the following beneficial effects: (1) The present application is prepared by the hydroxyl of double-end hydroxypropyl silicone oil, 2,6-piperazine diethanol, dimethyl ethanedione, the isocyanate group of hexamethylene diisocyanate is prepolymers, and the hydroxyl of pentaerythritol triacrylate is reacted to obtain silicone modified polyurethane acrylate, the structure of which contains-Si-O-Si- chain segment, the surface energy of which is low, the hydrophobicity of which is good, the interface / surface migration of which is formed during curing to form a dense hydrophobic film, which can block the penetration of water molecules, avoid the swelling of the adhesive layer and the decrease of the bonding force, and the structure is not easy to degrade at high temperature, maintain the integrity of the structure, prevent thermal shrinkage and micro-cracks; the polyurethane segment contains polar urethane groups, which can form interaction with the surface of the substrate to enhance the interfacial adhesion, reduce the interfacial gap, and relieve thermal stress through hydrogen bonding at high temperature; and the piperazine ring introduced by 2,6-piperazine diethanol is a rigid heterocyclic structure, which can improve the thermal deformation temperature of the molecular chain and enhance the structural stability of the material at high temperature, and the oxime group of dimethyl ethanedione can form hydrogen bond with the hydroxyl group on the surface of the substrate to enhance the interfacial bonding force and avoid interfacial peeling under high temperature and high humidity.

[0021] (2) The acrylate double bond in the molecular chain of the silicone modified polyurethane acrylate of the present application realizes photothermal dual curing with bisphenol A type epoxy resin, under the action of photoinitiator, the acrylate double bond is rapidly polymerized to form a preliminary crosslinked network, which fixes the morphology of the adhesive layer; with the increase of temperature, the acrylate crosslinked network and the epoxy groups of the epoxy resin further react to form a dense interpenetrating crosslinked network, which can greatly reduce the penetration channel of water molecules, and at the same time improve the thermal stability of the adhesive layer, avoid the decrease of sealing performance caused by softening of the adhesive layer at high temperature. In addition, the double bond or epoxy group in the silane coupling agent will also participate in the curing reaction, which can improve the crosslinking density and greatly enhance the bonding force of the sealant, and the sealing performance is better.

[0022] (3) The silicone modified polyurethane acrylate of the present application can form coordination between zinc ions and zinc-containing compounds, further densifying the interpenetrating crosslinked network, which helps to strengthen the sealing performance of the sealant.

[0023] (4) The preparation method of the sealant of the present application is simple, the raw materials are easy to obtain, the cost is low, the obtained sealant can still maintain excellent bonding performance under high temperature and high humidity environment, the sealing performance is greatly enhanced, the liquid crystal is well prevented from being contaminated, and the yield of liquid crystal display products is improved. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the present application will be described below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application.

[0025] Examples 1-5 provide a high-sealing photothermal dual-curing sealant and its preparation method.

[0026] Example 1 A high-sealing photothermal dual-curing sealant comprises the following raw materials in parts by weight: 60 parts of bisphenol A type epoxy resin (E51), 10 parts of silicone-modified polyurethane acrylate, 10 parts of filler, 5 parts of zinc-containing compound, 0.1 parts of curing agent, 1 part of photoinitiator, 1 part of silane coupling agent, and 15 parts of organic solvent. The preparation method of silicone-modified polyurethane acrylate is as follows: 100g of hydroxypropyl diethyl ester (molecular weight 500, hydroxyl content 4.5wt%), 17g of 2,6-piperazine diethanol, 2.3g of dimethyl oxime, and 0.2g of organotin (dibutyltin dilaurate) are added to 80g of acetone. After dehydration under reduced pressure, 60g of hexamethylene diisocyanate is added dropwise through a constant pressure dropping funnel under stirring, and the addition is completed within 1 hour. The mixture is then refluxed at 60℃ for 2 hours to obtain a prepolymer. Subsequently, 60g of pentaerythritol triacrylate and 0.2g of polymerization inhibitor (acryloylmorpholine) are added to the prepolymer. The mixture is heated to 75℃ and refluxed for 3 hours. After cooling to room temperature, the mixture is discharged to obtain silicone-modified polyurethane acrylate. The filler is talc; the zinc-containing compound is zinc stearate; the curing agent is 4,4'-diaminodiphenyl sulfone; the photoinitiator is ethyl 2,4,6-trimethylbenzoylphenylphosphonate; the silane coupling agent is methacryloxypropyltrimethoxysilane; and the organic solvent is acetone. A method for preparing a high-sealing photothermal dual-curing sealant includes the following steps: S1. After mixing bisphenol A type epoxy resin and organosilicon modified polyurethane acrylate, stir evenly to obtain mixture one; S2. Add the filler, zinc-containing compound, and silane coupling agent to the organic solvent, stir evenly, and cool to room temperature to obtain mixture two. S3. Add mixture 2 to mixture 1, mix well, add photoinitiator and curing agent, stir well to obtain mixture 3; S4. Grind the mixture three, filter, degas, and store in the dark to obtain the sealing adhesive.

[0027] Example 2 A high-sealing photothermal dual-curing sealant comprises the following raw materials in parts by weight: 70 parts of bisphenol A type epoxy resin (E51), 15 parts of silicone-modified polyurethane acrylate, 13 parts of filler, 7 parts of zinc-containing compound, 0.5 parts of curing agent, 2 parts of photoinitiator, 2 parts of silane coupling agent, and 20 parts of organic solvent. The preparation method of the organosilicon modified polyurethane acrylate is as follows: 100 g of double-end hydroxypropyl silicone oil (molecular weight 1000, hydroxyl content 2.5 wt%), 20 g of 2,6-piperazine diethanol, 3.0 g of dimethyl ethanedione, and 0.4 g of organic tin (stannous octoate) are added into 100 g of acetone, and after dehydration under reduced pressure, 45 g of hexamethylene diisocyanate is added dropwise through a constant-pressure dropping funnel under stirring within 1 h, and the reaction is carried out at 62 DEG C under reflux for 2.5 h to obtain a prepolymer; then 50 g of pentaerythritol triacrylate and 0.3 g of a polymerization inhibitor (phenothiazine) are added into the prepolymer, the temperature is raised to 78 DEG C, and the reaction is carried out under reflux for 4 h, and then the product is cooled to room temperature to obtain the organosilicon modified polyurethane acrylate; The filler is kaolin, the zinc-containing compound is zinc acetate, the curing agent is aniline, the photoinitiator is 4-acryloyloxybenzophenone, the silane coupling agent is 3-glycidyl ether oxypropyl trimethoxysilane, and the organic solvent is a mixture of isopropyl alcohol and acetone in a mass ratio of 1:1; A preparation method of a high-sealing photothermal dual-curing frame sealant, comprising the following steps: S1, mixing bisphenol A type epoxy resin and organosilicon modified polyurethane acrylate, stirring uniformly to obtain mixture one; S2, adding filler, zinc-containing compound, and silane coupling agent into organic solvent, stirring uniformly, and cooling to room temperature to obtain mixture two; S3, adding mixture two into mixture one, mixing uniformly, adding photoinitiator and curing agent, and stirring uniformly to obtain mixture three; S4, grinding mixture three, filtering, defoaming, and storing in the dark to obtain the frame sealant.

[0028] Example 3 A high-sealing photothermal dual-curing frame sealant, comprising the following raw materials in parts by weight: bisphenol A type epoxy resin (E51) 80 parts, organosilicon modified polyurethane acrylate 20 parts, filler 15 parts, zinc-containing compound 8 parts, curing agent 1 part, photoinitiator 3 parts, silane coupling agent 3 parts, and organic solvent 24 parts; The preparation method of the organosilicon modified polyurethane acrylate is as follows: 100 g of double-end hydroxypropyl silicone oil (molecular weight 1000, hydroxyl content 2.5 wt%), 20 g of 2,6-piperazine diethanol, 3.0 g of dimethyl ethanedione, and 0.4 g of organic tin (stannous octoate) are added into 100 g of acetone, and after dehydration under reduced pressure, 45 g of hexamethylene diisocyanate is added dropwise through a constant-pressure dropping funnel under stirring within 1 h, and the reaction is carried out at 62 DEG C under reflux for 2.5 h to obtain a prepolymer; then 50 g of pentaerythritol triacrylate and 0.3 g of a polymerization inhibitor (phenothiazine) are added into the prepolymer, the temperature is raised to 78 DEG C, and the reaction is carried out under reflux for 4 h, and then the product is cooled to room temperature to obtain the organosilicon modified polyurethane acrylate; The filler is magnesium hydroxide; the zinc-containing compound is zinc triflate; the curing agent is N,N'-dimethylethylenediamine; the photoinitiator is benzophenone; the silane coupling agent is obtained by mixing methacryloxypropyltrimethoxysilane and 3-glycidyloxypropyltrimethoxysilane at a mass ratio of 1:1; and the organic solvent is obtained by mixing acetone and N,N-dimethylformamide at a mass ratio of 1:1; A preparation method of a high-sealing photothermal dual-curing frame sealant, comprising the following steps: S1, mixing bisphenol A type epoxy resin and silicone modified polyurethane acrylate, stirring uniformly to obtain mixture one; S2, adding filler, zinc-containing compound and silane coupling agent into organic solvent, stirring uniformly, cooling to room temperature to obtain mixture two; S3, adding mixture two into mixture one, mixing uniformly, adding photoinitiator and curing agent, stirring uniformly to obtain mixture three; S4, grinding mixture three, filtering, defoaming, and shielding light to store to obtain frame sealant.

[0029] Example 4 A high-sealing photothermal dual-curing frame sealant, comprising the following raw materials by weight: bisphenol A type epoxy resin (E51) 90 parts, silicone modified polyurethane acrylate 25 parts, filler 18 parts, zinc-containing compound 8 parts, curing agent 1.5 parts, photoinitiator 4 parts, silane coupling agent 4 parts, and organic solvent 25 parts; The preparation method of the silicone modified polyurethane acrylate is as follows: 100 g of double-end hydroxypropyl silicone oil (molecular weight 500, hydroxyl content 4.5 wt%), 30 g of 2,6-piperazine diethanol, 5.5 g of dimethyl ethanedione, and 0.8 g of organic tin (stannous octoate) are added into 130 g of acetone, and then dehydrated under reduced pressure. Then, 80 g of hexamethylene diisocyanate is added dropwise into the mixture through a constant pressure dropping funnel under stirring within 1 h, and the mixture is refluxed at 70 ℃ for 3 h to obtain a prepolymer. Then, 75 g of pentaerythritol triacrylate and 0.5 g of a polymerization inhibitor (acryloyl morpholine) are added into the prepolymer, and the mixture is heated to 82 ℃, and then refluxed for 5 h to obtain the silicone modified polyurethane acrylate. The filler is silicon dioxide; the zinc-containing compound is zinc acetate; the curing agent is methoxyaniline; the photoinitiator is 4-acryloyloxybenzophenone; the silane coupling agent is obtained by mixing methacryloxypropyltrimethoxysilane and 3-glycidyloxypropyltrimethoxysilane at a mass ratio of 3:1; and the organic solvent is obtained by mixing isopropyl alcohol and ethyl acetate at a mass ratio of 1:1; A preparation method of a high-sealing photothermal dual-curing frame sealant, comprising the following steps: S1, the bisphenol A type epoxy resin and organic silicon modified polyurethane acrylate are mixed, stirred uniformly, and mixture one is obtained; S2, the filler, zinc-containing compound and silane coupling agent are added to the organic solvent, stirred uniformly, and cooled to room temperature to obtain mixture two; S3, mixture two is added to mixture one, mixed uniformly, and then the photoinitiator and curing agent are added and stirred uniformly to obtain mixture three; S4, the mixture three is ground, filtered and defoamed, and then stored in the dark to obtain the frame sealant.

[0030] Example 5 A high-sealing light-heat dual-curing frame sealant, comprising the following raw materials by weight: bisphenol A type epoxy resin (E51) 100 parts, organic silicon modified polyurethane acrylate 30 parts, filler 20 parts, zinc-containing compound 10 parts, curing agent 2 parts, photoinitiator 6 parts, silane coupling agent 5 parts, and organic solvent 30 parts. The preparation method of the organic silicon modified polyurethane acrylate is as follows: 100 g of double-end hydroxypropyl silicone oil (molecular weight 1000, hydroxyl content 2.5 wt%), 35 g of 2,6-piperazine diethanol, 6.9 g of dimethyl ethanedione, and 1.0 g of organic tin (dibutyl tin dilaurate) are added to 150 g of acetone, and then dehydrated under reduced pressure. Under the condition of stirring, 75 g of hexamethylene diisocyanate is added dropwise through a constant pressure dropping funnel within 1 h, and then refluxed at 70℃ for 3 h to obtain a prepolymer. Then 70 g of pentaerythritol triacrylate and 0.6 g of polymerization inhibitor (acryloyl morpholine) are added to the prepolymer, and then heated to 85℃. After refluxing for 6 h, the mixture is cooled to room temperature and discharged to obtain the organic silicon modified polyurethane acrylate. The filler is silicon dioxide; the zinc-containing compound is zinc triflate; the curing agent is obtained by mixing aniline and 4,4'-diamino diphenyl ether in a mass ratio of 1:2; the photoinitiator is 2,4,6-trimethyl benzoyl phenyl phosphonic acid ethyl ester; the silane coupling agent is obtained by mixing methacryloyl oxypropyl trimethoxysilane and 3-glycidyl ether oxypropyl trimethoxysilane in a mass ratio of 1:4; and the organic solvent is acetone. A preparation method of a high-sealing light-heat dual-curing frame sealant, comprising the following steps: S1, the bisphenol A type epoxy resin and organic silicon modified polyurethane acrylate are mixed, stirred uniformly, and mixture one is obtained; S2, the filler, zinc-containing compound and silane coupling agent are added to the organic solvent, stirred uniformly, and cooled to room temperature to obtain mixture two; S3, mixture two is added to mixture one, mixed uniformly, and then the photoinitiator and curing agent are added and stirred uniformly to obtain mixture three; S4, the mixture three is ground, filtered and defoamed, and then stored in the dark to obtain the frame sealant.

[0031] In order to verify the performance of the sealant of the present application, Comparative Examples 1-4 are provided: Comparative Example 1 Comparative Example 1 is the same as Example 1 except that the silicone-modified polyurethane acrylate is YC5016 (Shanghai Yinchang New Material Co., Ltd.), which is as follows: A high-sealing light-thermal dual-curing sealant, comprising the following raw materials by weight: bisphenol A type epoxy resin (E51) 60 parts, silicone-modified polyurethane acrylate 10 parts, filler 10 parts, zinc-containing compound 5 parts, curing agent 0.1 part, photoinitiator 1 part, silane coupling agent 1 part, organic solvent 15 parts; The silicone-modified polyurethane acrylate is YC5016 (Shanghai Yinchang New Material Co., Ltd.); the filler is talc; the zinc-containing compound is zinc stearate; the curing agent is 4,4'-diamino diphenyl sulfone; the photoinitiator is 2,4,6-trimethylbenzoyl phenyl phosphonic acid ethyl ester; the silane coupling agent is methacryloyloxypropyl trimethoxysilane; and the organic solvent is acetone. A preparation method of a high-sealing light-thermal dual-curing sealant, comprising the following steps: S1, mixing bisphenol A type epoxy resin and silicone-modified polyurethane acrylate, stirring uniformly to obtain mixture one; S2, adding filler, zinc-containing compound, and silane coupling agent to the organic solvent, stirring uniformly, and cooling to room temperature to obtain mixture two; S3, adding mixture two to mixture one, mixing uniformly, adding photoinitiator and curing agent, and stirring uniformly to obtain mixture three; S4, grinding mixture three, filtering, defoaming, and storing in the dark to obtain the sealant.

[0032] Comparative Example 2 Comparative Example 2 is the same as Example 1 except that the preparation method of the silicone-modified polyurethane acrylate is different and no dimethyl ethanedione is added, which is as follows: A high-sealing light-thermal dual-curing sealant, comprising the following raw materials by weight: bisphenol A type epoxy resin (E51) 60 parts, silicone-modified polyurethane acrylate 10 parts, filler 10 parts, zinc-containing compound 5 parts, curing agent 0.1 part, photoinitiator 1 part, silane coupling agent 1 part, organic solvent 15 parts; The preparation method of the organosilicon-modified polyurethane acrylate is as follows: 100 g of double-end hydroxypropyl silicone oil (molecular weight 500, hydroxyl content 4.5 wt%) and 17 g of 2,6-piperazine diethanol are added to 80 g of acetone, and after dehydration under reduced pressure, 60 g of hexamethylene diisocyanate is added dropwise through a constant-pressure dropping funnel under stirring within 1 h, and reflux reaction is performed at 60 DEG C for 2 h to obtain a prepolymer; then 60 g of pentaerythritol triacrylate and 0.2 g of an inhibitor (acryloyl morpholine) are added to the prepolymer, and after being warmed to 75 DEG C, reflux reaction is performed for 3 h, and then the mixture is cooled to room temperature to obtain the organosilicon-modified polyurethane acrylate; The filler is talc; the zinc-containing compound is zinc stearate; the curing agent is 4,4'-diamino diphenyl sulfone; the photoinitiator is 2,4,6-trimethylbenzoyl phenyl phosphonic acid ethyl ester; the silane coupling agent is methacryloyloxypropyl trimethoxysilane; and the organic solvent is acetone; A preparation method of a high-sealing photothermal dual-curing frame sealant, comprising the following steps: S1, mixing bisphenol A type epoxy resin and organosilicon-modified polyurethane acrylate, and stirring uniformly to obtain mixture one; S2, adding the filler, the zinc-containing compound, and the silane coupling agent into the organic solvent, stirring uniformly, and cooling to room temperature to obtain mixture two; S3, adding mixture two into mixture one, mixing uniformly, adding the photoinitiator and the curing agent, and stirring uniformly to obtain mixture three; S4, grinding mixture three, filtering, defoaming, and storing in the dark to obtain the frame sealant.

[0033] Comparative Example 3 Comparative Example 3 is different from Example 1 in that the preparation method of the organosilicon-modified polyurethane acrylate is different, and 2,6-piperazine diethanol is not added, and the specific method is as follows: A high-sealing photothermal dual-curing frame sealant comprises the following raw materials by weight: 60 parts of bisphenol A type epoxy resin (E51), 10 parts of organosilicon-modified polyurethane acrylate, 10 parts of filler, 5 parts of zinc-containing compound, 0.1 parts of curing agent, 1 part of photoinitiator, 1 part of silane coupling agent, and 15 parts of organic solvent; The preparation method of the organosilicon-modified polyurethane acrylate is as follows: 100 g of double-end hydroxypropyl silicone oil (molecular weight 500, hydroxyl content 4.5 wt%), 2.3 g of dimethyl ethanedione, and 0.2 g of organic tin (dibutyl tin dilaurate) are added into 80 g of acetone, and after dehydration under reduced pressure, 60 g of hexamethylene diisocyanate is added dropwise through a constant-pressure dropping funnel under stirring within 1 h, and reflux reaction is performed at 60°C for 2 h to obtain a prepolymer; then 60 g of pentaerythritol triacrylate and 0.2 g of a polymerization inhibitor (acryloyl morpholine) are added into the prepolymer, the temperature is raised to 75°C, and after reflux reaction is performed for 3 h, the mixture is cooled to room temperature to obtain the organosilicon-modified polyurethane acrylate; The filler is talc; the zinc-containing compound is zinc stearate; the curing agent is 4,4'-diamino diphenyl sulfone; the photoinitiator is 2,4,6-trimethylbenzoyl phenyl phosphonic acid ethyl ester; the silane coupling agent is methacryloyloxypropyl trimethoxysilane; and the organic solvent is acetone; A preparation method of a high-sealing photothermal dual-curing frame sealant, comprising the following steps: S1, mixing bisphenol A type epoxy resin and organosilicon-modified polyurethane acrylate, and stirring uniformly to obtain mixture one; S2, adding the filler, the zinc-containing compound, and the silane coupling agent into the organic solvent, stirring uniformly, and cooling to room temperature to obtain mixture two; S3, adding mixture two into mixture one, mixing uniformly, adding the photoinitiator and the curing agent, and stirring uniformly to obtain mixture three; S4, grinding mixture three, filtering, defoaming, and storing in the dark to obtain the frame sealant.

[0034] Comparative Example 4 Comparative Example 4 is the same as Example 1 except that no zinc-containing compound is added, and the specific process is as follows: A high-sealing photothermal dual-curing frame sealant, comprising the following raw materials by weight: 60 parts of bisphenol A type epoxy resin (E51), 10 parts of organosilicon-modified polyurethane acrylate, 10 parts of filler, 0.1 part of curing agent, 1 part of photoinitiator, 1 part of silane coupling agent, and 15 parts of organic solvent; The preparation method of the organosilicon-modified polyurethane acrylate is as follows: 100 g of double-end hydroxypropyl silicone oil (molecular weight 500, hydroxyl content 4.5 wt%), 17 g of 2,6-piperazine diethanol, 2.3 g of dimethyl ethanedione, and 0.2 g of organic tin (dibutyl tin dilaurate) are added to 80 g of acetone, and after dehydration under reduced pressure, 60 g of hexamethylene diisocyanate is added dropwise through a constant-pressure dropping funnel under stirring within 1 h, and reflux reaction is performed at 60°C for 2 h to obtain a prepolymer; then 60 g of pentaerythritol triacrylate and 0.2 g of a polymerization inhibitor (acryloyl morpholine) are added to the prepolymer, the temperature is raised to 75°C, and reflux reaction is performed for 3 h, and then the mixture is cooled to room temperature to obtain the organosilicon-modified polyurethane acrylate; The filler is talc; the curing agent is 4,4'-diamino diphenyl sulfone; the photoinitiator is 2,4,6-trimethylbenzoyl phenyl phosphonic acid ethyl ester; the silane coupling agent is methacryloyloxypropyl trimethoxysilane; and the organic solvent is acetone; A preparation method of a high-sealing photothermal dual-curing frame sealant, comprising the following steps: S1, mixing bisphenol A type epoxy resin and organosilicon-modified polyurethane acrylate, and stirring uniformly to obtain mixture one; S2, adding the filler and the silane coupling agent to the organic solvent, stirring uniformly, and cooling to room temperature to obtain mixture two; S3, adding mixture two to mixture one, mixing uniformly, adding the photoinitiator and the curing agent, and stirring uniformly to obtain mixture three; S4, grinding mixture three, filtering, defoaming, and storing in the dark to obtain the frame sealant.

[0035] Performance test Bonding performance: the frame sealant is coated on the upper surface of A glass in the center, B glass is perpendicular to A glass and the central position is attached to the frame sealant, the frame sealant is spread after attachment, and 100 mW / cm 2 of ultraviolet light is irradiated for 30 s, and then heated at 100°C for 50 min to obtain a bonding test piece, and the bonding strength of the obtained bonding test piece is determined by using a universal testing machine; A glass and B glass are both ITO glass substrates with a size specification of 25 mm x 40 mm x 0.7 mm; High temperature and high humidity resistance: (1) the same method as described above was used to prepare adhesive test pieces, which were placed in an environment with a temperature of 85°C and a relative humidity of 85% for 240h, 480h, and 720h, and then the adhesive strength was tested. The adhesive strength loss rate was calculated by comparing the original adhesive strength; (2) the sealant was used to prepare a liquid crystal cell, which was placed in an environment with a temperature of 85°C and a relative humidity of 85% for 240h, 480h, and 720h. The liquid crystal was observed under a polarizer. If there was no blue-purple halo phenomenon, it indicated that the liquid crystal was not contaminated, and was marked as ■. If there was a blue-purple halo phenomenon, it indicated that the liquid crystal was contaminated, and was marked as ▲. Moisture permeability: the sealant was first irradiated with 100mW / cm2 2 ultraviolet light for 30s, then heated at 100°C for 50min, and then cooled to room temperature. The film with a diameter of 55mm and a thickness of 300μm was cut. The film was placed in a moisture permeation cup, and calcium chloride was added. The moisture permeation cup was placed in an environment with a temperature of 85°C and a relative humidity of 85% for 480h. The moisture permeability was calculated by dividing the water absorption of calcium chloride by the area of the film.

[0036] The performance test results are shown in Tables 1 and 2.

[0037] Table 1:

[0038] Table 2:

[0039] As shown in Tables 1 and 2, the adhesive properties, high temperature and high humidity resistance, and moisture permeability of the sealant obtained in Examples 1-5 are significantly better than those of Comparative Examples 1-4. Among them, Comparative Example 1 and Comparative Example 1 fully illustrate that the silicone-modified polyurethane acrylate of the present application is more helpful than the silicone-modified polyurethane acrylate of the prior art in improving the overall performance of the sealant; Comparative Example 1 and Comparative Example 2, 3 illustrate that 2, 6-piperazine diethanol and dimethyl ethanedione are beneficial to enhancing the high temperature and high humidity resistance of the silicone-modified polyurethane acrylate, and thus greatly improve the sealing performance of the sealant; Comparative Example 1 and Comparative Example 4 illustrate that the zinc-containing compound in the formula of the sealant interacts with other components, significantly improving the moisture permeability and high temperature and high humidity resistance of the sealant, so that the sealant can well block the entry of water vapor and oxygen, preventing the liquid crystal from being contaminated.

[0040] It should be noted that the above disclosed embodiments only illustrate the technical solutions of the present application, and are not intended to limit the protection scope of the present application. Although the present application is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that any modifications or various changes, equivalent replacements within the scope of the technical solutions of the present application should all fall within the protection scope of the present application.

Claims

1. A high-sealing photothermal dual-curing frame sealant, characterized in that, The raw materials include the following parts by weight: 60-100 parts of bisphenol A type epoxy resin, 10-30 parts of silicone-modified polyurethane acrylate, 10-20 parts of filler, 5-10 parts of zinc-containing compound, 0.1-2 parts of curing agent, 1-6 parts of photoinitiator, 1-5 parts of silane coupling agent, and 15-30 parts of organic solvent. The organosilicon-modified polyurethane acrylate is obtained by first reacting bi-terminated hydroxypropyl silicone oil, 2,6-piperazine diethanol, dimethylglyoxime and hexamethylene diisocyanate to form a prepolymer, and then reacting the prepolymer with pentaerythritol triacrylate. 2.The high-sealing optical-thermal dual-curing frame sealant of claim 1, wherein, The preparation method of the organosilicon-modified polyurethane acrylate is as follows: Bis(hydroxypropyl) silicone oil, 2,6-piperazine diethanol, dimethylglyoxime, and organotin were added to acetone and dehydrated under reduced pressure. Hexamethylene diisocyanate was then added dropwise through a constant-pressure dropping funnel under stirring, with the addition completed within 1 hour. The mixture was then refluxed at 60-70°C for 2-3 hours to obtain a prepolymer. Subsequently, pentaerythritol triacrylate and a polymerization inhibitor were added to the prepolymer, and the mixture was heated to 75-85°C and refluxed for 3-6 hours. After cooling to room temperature, the product was discharged to obtain organosilicon-modified polyurethane acrylate. 3.The high-sealing optical-thermal dual-curing frame sealant of claim 2, wherein, The mass ratio of the dual-terminated hydroxypropyl silicone oil, 2,6-piperazine diethanol, dimethyl ethylenedioxime, hexamethylene diisocyanate, pentaerythritol triacrylate, organotin, polymerization inhibitor, and acetone is 100:(17-35):(2.3-6.9):(45-80):(40-75):(0.2-1.0):(0.2-0.6):(80-150). 4.The high-sealing optical-thermal dual-curing frame sealant of claim 3, wherein, The molecular weight of the double-ended hydroxypropyl silicone oil is 500-2000, and the hydroxyl content is 1.5wt%-5wt%. 5.The high-sealing optical-thermal dual-curing frame sealant of claim 4, wherein, The organotin is one or more of stannous octoate, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin acetate; the polymerization inhibitor is one or more of p-hydroxyanisole, acrylmorpholine, and phenothiazine. 6.The high-sealing optical-thermal dual-curing frame sealant of claim 1, wherein, The filler is one or more of the following: talc, kaolin, magnesium hydroxide, silicon dioxide, calcium carbonate, and calcium silicate. 7.The high-sealing optical-thermal dual-curing frame sealant of claim 1, wherein, The zinc-containing compound is one or more of zinc chloride, zinc sulfate, zinc stearate, zinc acetate, zinc trifluorosulfonate, and zinc acetylacetonate. 8.The high-sealing optical-thermal dual-curing frame sealant of claim 1, wherein, The curing agent is one or more of aniline, methoxyaniline, N,N'-dimethylethylenediamine, ethanolamine, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl ether; the photoinitiator is one or more of 2,4,6-trimethylbenzoylphenylphosphonate, 4-acryloyloxybenzophenone, 4-dimethylaminobenzoate, and benzophenone. 9.The high-sealing optical-thermal dual-curing frame sealant of claim 1, wherein, The silane coupling agent is methacryloyloxypropyltrimethoxysilane and / or 3-glycidyl etheroxypropyltrimethoxysilane.

10. A method for preparing the high-sealing photothermal dual-curing frame sealant according to any one of claims 1-9, characterized in that, Includes the following steps: S1. After mixing bisphenol A type epoxy resin and organosilicon modified polyurethane acrylate, stir evenly to obtain mixture one; S2. Add the filler, zinc-containing compound, and silane coupling agent to the organic solvent, stir evenly, and cool to room temperature to obtain mixture two. S3. Add mixture 2 to mixture 1, mix well, add photoinitiator and curing agent, stir well to obtain mixture 3; S4, grinding the mixture three, filtering, defoaming, light shielding, and obtaining the sealant.

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