CN115477900B - Acrylic optical adhesive with three-layer structure and preparation method thereof - Google Patents
Acrylic optical adhesive with three-layer structure and preparation method thereof Download PDFInfo
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
- C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
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Abstract
The invention discloses an acrylic optical adhesive with a three-layer structure and a preparation method thereof, wherein the acrylic optical adhesive sequentially comprises an OCA optical adhesive film, a modified OCA optical adhesive film and an OCA optical adhesive film from top to bottom; mixing water-soluble acrylic resin and hydroxyethyl acrylate, synthesizing a pretreatment solvent under the action of an initiator and a chain transfer agent, grafting 3-methacrylic acid propyl tri (trimethoxy silicon) to obtain OCA optical adhesive, further modifying by adopting polydimethyl diallyl amine chloride, compositing with isooctyl acrylate and glycidyl methacrylate to obtain modified OCA optical adhesive, and coating to obtain the acrylic optical adhesive. Compared with the prior art, the acrylic optical adhesive prepared by the invention has the advantages of enhancing thermal decomposition performance, improving bonding strength, improving light transmittance, along with simple and environment-friendly preparation method, and being suitable for being used as an adhesive of photoelectric devices.
Description
Technical Field
The invention relates to the technical field of optical cement, in particular to an acrylic optical cement with a three-layer structure and a preparation method thereof.
Background
The acrylic acid adhesive is a viscoelastic material based on acrylic acid monomer, and is adhered to various adherends in a short time at room temperature, does not generate chemical reaction, and has no residue after removal. Has the advantages of oxidation resistance, water resistance, no yellowing, transparency and the like, and can be widely applied to the industrial field, such as being used as an optical transparent adhesive for packaging adhesive tapes, medical pads, shielding adhesive tapes, protective films and hydrogels. However, general acrylic has various disadvantages such as low thermal stability to low surface energy substrates (e.g., polyethylene, polypropylene, and polydimethylsiloxane) and low adhesive strength. A common solution is to treat the substrate surface with corona, plasma or chemical agents. However, surface treatment can lead to a number of problems such as substrate damage, waste disposal and reduced light transmittance. Therefore, development of an acrylic optical adhesive with good thermal stability, strong adhesion and high light transmittance is very important.
The invention of China patent CN113755104A discloses and is applied to the optical cement of the composite three-layer structure of the flexible folding screen, the optical cement of the composite three-layer structure applied to the flexible folding screen sequentially comprises an SCA optical cement film, an elastic hybridization nanoparticle OCA optical cement film and an SCA optical cement film from top to bottom, and the SCA optical cement film is prepared by spraying an SCA hot melt adhesive on the surface of an adherend through a hot melt adhesive pipe and a hot melt adhesive gun of a hot melt adhesive machine and then ultraviolet curing; the elastic hybrid nano particle OCA optical adhesive film is prepared by attaching elastic hybrid nano particles on the surface of the OCA optical adhesive film in a grafting mode and reacting silicon dioxide nano particles with 3 (trimethoxy silicon based) propyl methacrylate. According to the technical scheme, the nano particles are attached to the OCA optical adhesive film, and two layers of SCA optical adhesive films are covered on the OCA optical adhesive film, so that the probability that white spots appear in the cured SCA optical adhesive film is greatly reduced. However, the optical cement with the three-layer structure prepared by the invention has poor thermal stability and low light transmittance.
The Chinese patent No. 108753182A discloses an OCA optical adhesive with excellent performance, which utilizes the compounding of acrylic acid-2-ethyl-1-dodecyl ester, phenoxybenzyl acrylate and N-vinylformamide to enable the characteristics of a high-temperature high-humidity monomer, a high-folding monomer and an adhesion promotion functional monomer to efficiently cooperate and show excellent compatibility and suitability, and further adjusts other raw material components to have higher adaptation degree, so that the OCA optical adhesive can be polymerized by adopting a controllable active polymerization method, thereby obtaining the OCA optical adhesive with excellent performance, and effectively solving the technical problems of screen brightness and contrast reduction, poor visual effect and the like caused by poor high-temperature and high-humidity resistance and wider molecular weight distribution of the traditional acrylic optical adhesive. However, the OCA optical adhesive prepared by the method still has poor thermal stability and insufficient adhesive strength.
Disclosure of Invention
In view of the defects of poor thermal stability, weak adhesiveness and low light transmittance of the acrylic optical adhesive in the prior art, the technical problem to be solved by the invention is to provide the acrylic optical adhesive with good thermal stability, strong adhesiveness and high light transmittance and the preparation method thereof.
In order to achieve the above object, the present invention adopts the following technical scheme:
the acrylic optical adhesive with the three-layer structure sequentially comprises an uppermost OCA optical adhesive film, a modified OCA optical adhesive film and a lowermost OCA optical adhesive film from top to bottom;
the lowest OCA optical adhesive film is obtained by coating OCA optical adhesive on a heavy release film;
the modified OCA optical adhesive film is obtained by coating a modified OCA optical adhesive on the lowest OCA optical adhesive film;
the uppermost OCA optical adhesive film is obtained by coating OCA optical adhesive on a modified OCA optical adhesive film;
the modified OCA optical adhesive is prepared by further modifying OCA optical adhesive.
The preparation method of the three-layer acrylic optical adhesive comprises the following steps:
uniformly coating OCA optical adhesive on a heavy release film, wherein the thickness is 20-40 mu m, ultraviolet curing to obtain a lowermost OCA optical adhesive film, coating modified OCA optical adhesive on the lowermost OCA optical adhesive film, coating the modified OCA optical adhesive film with the thickness of 30-50 mu m, ultraviolet curing to obtain a modified OCA optical adhesive film, coating OCA optical adhesive on the modified OCA optical adhesive film, coating the OCA optical adhesive film with the thickness of 20-40 mu m, ultraviolet curing, coating the uppermost OCA optical adhesive film to obtain a three-layer structure composite adhesive, further curing the three-layer structure composite adhesive by adopting a thermal baking mode, and attaching a light release film on the cured OCA optical adhesive film to obtain the three-layer structure acrylic optical adhesive.
Preferably, the temperature of the thermal baking and curing treatment is 80-120 ℃ and the time is 5-15 min.
Preferably, the preparation method of the OCA optical adhesive comprises the following steps of:
s1, mixing 0.5-1.5 parts of water-soluble acrylic resin and 0.05-0.2 part of hydroxyethyl acrylate, then adding 0.0005-0.002 part of photoinitiator and 0.0003-0.001 part of chain transfer agent, stirring and mixing for 2-5 hours at 20-30 ℃ by using a magnetic stirrer, wherein the stirring speed is 1000-2000 rpm, bubbling nitrogen for degassing for 20-50 min, and performing ultraviolet curing under a nitrogen atmosphere to obtain a pretreatment solvent;
s2, mixing 10-15 parts of 0.1-0.3wt% NaOH aqueous solution and the pretreatment solvent prepared in the step S1, stirring at 200-500 rpm for 10-50 min at room temperature to obtain a reaction solution, adding 0.5-2 parts of 3-propyl tri (trimethoxy silicon) methacrylate into the reaction solution at the addition rate of 1-3 mL/min, firstly stirring at room temperature for 5-15 h at the stirring speed of 100-300 rpm, and then stirring at the same speed at 40-60 ℃ for 10-20 h to obtain the OCA optical cement.
Preferably, the chain transfer agent is t-dodecyl mercaptan.
Preferably, the ultraviolet energy used for the ultraviolet curing is respectively and independently 200-1200 mJ/cm 2 。
The preparation method of the modified OCA optical adhesive comprises the following steps of:
adding 0.2-0.6 part of polydimethyldiallyl amine chloride into a container, mixing 0.01-0.03 part of diisocyanate and 0.0003-0.001 part of dibutyltin dilaurate under the nitrogen atmosphere at the temperature of 40-60 ℃, stirring and reacting for 30-50 min, then injecting 0.6-2 parts of OCA optical cement with the injection speed of 2-5 mL/min, stirring the reaction mixture for 30-50 min, and cooling to room temperature to obtain the pretreated optical cement; adding 0.03-0.08 part of isooctyl acrylate and 0.02-0.05 part of glycidyl methacrylate into 0.5-2 parts of ethyl acetate to prepare a reaction mixture, adding the pretreatment optical cement into the reaction mixture, stirring for 30-50 min at 70-100 ℃ under nitrogen atmosphere, wherein the stirring speed is 200-500 rpm, dripping 0.005-0.02 part of free radical initiator into the reaction mixture in the stirring process, the dripping speed is 0.5-2 mL/min, reacting for 4-8 h, and cooling to room temperature to obtain the modified OCA optical cement.
Preferably, the catalyst is dibutyl tin dilaurate.
Preferably, the free radical initiator is prepared by dissolving 0.3 to 1 weight part of azodiisobutyronitrile in 6 to 15 weight parts of ethyl acetate.
According to the invention, water-soluble acrylic resin and hydroxyethyl acrylate are mixed, a pretreatment solvent is synthesized under the action of an initiator and a chain transfer agent, then 3-methyl acrylic propyl tri (trimethoxy silicon) is grafted to obtain OCA optical adhesive, polydimethyl diallyl amine chloride is further adopted for modification, and the OCA optical adhesive is compounded with isooctyl acrylate and glycidyl methacrylate to obtain modified OCA optical adhesive, and the acrylic optical adhesive is prepared through coating. The increase in the thermal weight loss temperature is because the reaction proceeds by adding a certain amount of NaOH aqueous solution and reaction solvent during the preparation of the acrylic optical adhesive, by providing an alkaline reaction environment and reducing the optical adhesive, so that the mass loss of the acrylic optical adhesive occurring at the initial stage of thermal decomposition is due to volatilization of the solvent. When the temperature continues to rise, the optical cement is decomposed secondarily, and at the moment, the main component acrylic resin in the optical cement is thermally cracked, molecular chains are unfolded, and adverse effects such as yellowing, atomization and the like are generated. The hydroxyethyl acrylate side chain consists of hydrophilic and hydrophobic segments, and is combined with water-soluble acrylic resin to form a simple linear entangled spiral structure due to high flexibility, polarity and chain length, so that free volume is reduced, a compact inter-chain structure is formed, and the entanglement of the chain structure and physical crosslinking formed by secondary bonding of the hydroxyethyl acrylate side chain inhibit the damage of the chain caused by heating, so that the thermal weight loss temperature is increased. The 3-methacrylic acid propyl tri (trimethoxy silicon) is fixed on the spiral structure through grafting and generates hydrogen bond interaction with silanol groups, so that the fluidity of the spiral chain is reduced, the cohesive strength of the material is increased, the stacking density is higher, and the thermal weightlessness temperature is further improved. The polydimethyl diallyl amine chloride is modified and is compounded with the isooctyl acrylate and the glycidyl methacrylate to form a semi-interpenetrating network structure, a heated damage mode is changed from cohesive damage to adhesive damage and then cohesive damage, the thermal weight loss temperature of the middle-layer modified OCA optical adhesive is improved, the synergistic effect of the mixed reactions enhances the thermal weight loss temperature of the acrylic optical adhesive, and the thermal stability is higher in the use process.
The physical crosslinking generated by entanglement and secondary bonding of the chain structure generates good cohesiveness, so that the adhesive strength is high, and the synthetic acrylic optical adhesive has lower modulus and larger contact area of materials. 3-propyl tris (trimethoxy silicon) methacrylate can improve bond strength by providing cohesive strength and energy dissipation; however, poor adhesion results from poor miscibility of isooctyl acrylate and glycidyl methacrylate with OCA optical cement. But due to the connection of the polydimethyl diallyl ammonium chloride, the miscibility of the OCA optical adhesive with the isooctyl acrylate and the glycidyl methacrylate is improved, so that the OCA optical adhesive has better bonding strength with the OCA optical adhesive.
The material adopted by the invention has better transparent property, the gaps among molecules are reduced by improving the miscibility, the light transmittance of the material is improved by modifying the OCA optical adhesive to form a semi-interpenetrating network structure, and the material is used as an intermediate layer for coating, so that the light transmittance of the whole acrylic optical adhesive can be improved, and the material is more suitable for photoelectric devices.
Compared with the prior art, the invention has the beneficial effects that:
1) According to the invention, water-soluble acrylic resin and hydroxyethyl acrylate are mixed, a pretreatment solvent is synthesized under the action of an initiator and a chain transfer agent, then 3-methyl acrylic propyl tri (trimethoxy silicon) is grafted to obtain OCA optical adhesive, polydimethyl diallyl amine chloride is further adopted for modification, and the OCA optical adhesive is compounded with isooctyl acrylate and glycidyl methacrylate to obtain modified OCA optical adhesive, and the acrylic optical adhesive is prepared through coating. The thermal decomposition performance of the acrylic optical adhesive is enhanced, the bonding strength is improved, and the light transmittance is improved;
2) The invention adopts a scientific preparation method to compound the OCA optical adhesive and the modified OCA optical adhesive to prepare the acrylic optical adhesive with a three-layer structure, the preparation method is simple and environment-friendly, the material distribution is reasonable, and the acrylic optical adhesive is suitable for being used as an adhesive of photoelectric devices.
Detailed Description
The technical scheme of the present invention will be described in detail by means of specific examples, which should be explicitly set forth for illustration, but should not be construed as limiting the scope of the present invention.
The parameters of partial raw materials in the embodiment of the invention are as follows:
water-soluble acrylic resin, the model of the new material Co., ltd., in the city of Buddha: JT-207A with content more than or equal to 55%;
photoinitiator, chongqing new material limited company, model: 184D, cargo number: AL-620474610153, active substance content: 99.9%;
diisocyanate, shanghai North chemical engineering Co., ltd., model: aqueous IPDI;
polydimethyldiallylamine chloride, wuhan Ke Mike biomedical technologies Co., ltd., product number: whkmk-8695432, active substance content: 40%, CAS:26062-79-3;
heavy release film, huizhongda technology Co., ltd., material: BOPET, thickness: 38 um-150 um, type transparent film, release force: 25-30 g;
light release film, dongguan city Wenfeng composite material Co., ltd., product number: WFM0025, material: PET film, thickness: 0.025mm;
acrylic adhesive, shanghai Sen Van Co., ltd., model: 349, viscosity: 13500 pa.s.
Example 1
An acrylic optical adhesive with a three-layer structure is prepared by the following steps:
uniformly coating OCA optical adhesive on the heavy release film by using a coating machine, wherein the thickness is 30 mu m, the ultraviolet curing is carried out, and the ultraviolet energy is 800mJ/cm 2 Obtaining the lowest OCA optical adhesive film, coating the modified OCA optical adhesive on the lowest OCA optical adhesive film, wherein the coating thickness is 40 mu m, and the ultraviolet curing and the ultraviolet energy are 800mJ/cm 2 Obtaining a modified OCA optical adhesive film, then coating OCA optical adhesive on the modified OCA optical adhesive film, wherein the coating thickness is 30 mu m, the ultraviolet curing is carried out, and the ultraviolet energy is 800mJ/cm 2 The coating layer is the uppermost OCA optical adhesive film, the three-layer structure composite adhesive is obtained, the three-layer structure composite adhesive is further cured by adopting a hot baking mode, the temperature of the hot baking curing treatment is 100 ℃, the baking time is 10min, and the cured OCA optical adhesive film is stuck with a light release film, so that the three-layer structure acrylic optical adhesive is obtained.
The preparation method of the OCA optical adhesive comprises the following steps:
s1, adding 900g of water-soluble acrylic resin and 100g of hydroxyethyl acrylate into a three-necked flask, then adding 1g of photoinitiator and 0.5g of tertiary dodecyl mercaptan, stirring and mixing for 3 hours at 25 ℃ by a magnetic stirrer at a stirring speed of 1200rpm, bubbling with nitrogen for degassing for 30min, and curing by ultraviolet rays under a nitrogen atmosphere, wherein the ultraviolet ray energy is 400mJ/cm 2 Obtaining a pretreatment solvent;
s2, 13kg of 0.2wt% NaOH aqueous solution and the pretreatment solvent prepared in the step S1 are poured into a four-necked flask to be mixed, then stirred at 250rpm for 30min at room temperature, then 1kg of 3-propyl tri (trimethoxy silicon) methacrylate is added into the four-necked flask, the adding rate is 2mL/min, firstly, the mixture is stirred at room temperature for 10h, the stirring rate is 200rpm, and then the mixture is stirred at the same speed for 14h at 50 ℃ to obtain the OCA optical cement.
The preparation method of the modified OCA optical adhesive comprises the following steps:
adding 400g of polydimethyl diallyl amine chloride into a double-neck flask, mixing 20g of diisocyanate and 0.5g of dibutyltin dilaurate under the nitrogen atmosphere at 50 ℃, stirring for reaction for 40min, injecting 1kg of OCA optical cement with the injection speed of 3mL/min, stirring for 40min, and cooling to room temperature to obtain pretreated optical cement; 65g of isooctyl acrylate and 35g of glycidyl methacrylate are added into 1kg of ethyl acetate to prepare a reaction mixture, the pretreatment optical cement is added into the reaction mixture and stirred for 40min under the nitrogen atmosphere at 80 ℃, the stirring speed is 300rpm, and a free radical initiator prepared by dissolving 0.5g of azobisisobutyronitrile into 9.5g of ethyl acetate in the stirring process is dripped into the reaction mixture at the dripping speed of 1mL/min, and after the reaction for 6h, the reaction mixture is cooled to room temperature to obtain the modified OCA optical cement.
Example 2
The preparation method of the three-layer acrylic optical adhesive is basically the same as that of example 1, except that: the preparation methods of the OCA optical adhesive are different.
The preparation method of the OCA optical adhesive comprises the following steps:
s1, adding 900g of water-soluble acrylic resin into a three-necked flask, then adding 1g of photoinitiator and 0.5g of tertiary dodecyl mercaptan, stirring and mixing for 3 hours at 25 ℃ by a magnetic stirrer at 1200rpm, bubbling with nitrogen for 30min, and curing by ultraviolet rays under a nitrogen atmosphere, wherein the ultraviolet energy is 400mJ/cm 2 Obtaining an acrylic resin solvent;
s2, 13kg of a 0.2wt% NaOH aqueous solution and the acrylic resin solvent prepared in the step S1 are poured into a four-necked flask to be mixed, then stirred at 250rpm for 30min at room temperature, then 1kg of 3-propyl tri (trimethoxy silicon) methacrylate is added into the four-necked flask, the adding rate is 2mL/min, firstly, the stirring is carried out at room temperature for 10h, the stirring speed is 200rpm, and then the stirring is carried out at 50 ℃ for 14h at the same speed, so that the OCA optical cement is obtained.
The preparation method of the modified OCA optical adhesive is the same as that of example 1.
Example 3
The preparation method of the three-layer acrylic optical adhesive is basically the same as that of example 1, except that: the preparation methods of the OCA optical adhesive are different.
The preparation method of the OCA optical adhesive comprises the following steps:
s1, adding 900g of water-soluble acrylic resin and 100g of hydroxyethyl acrylate into a three-necked flask, then adding 1g of photoinitiator and 0.5g of tertiary dodecyl mercaptan, stirring and mixing for 3 hours at 25 ℃ by a magnetic stirrer at a stirring speed of 1200rpm, bubbling with nitrogen for degassing for 30min, and curing by ultraviolet rays under a nitrogen atmosphere, wherein the ultraviolet ray energy is 400mJ/cm 2 Obtaining a pretreatment solvent;
s2, 13kg of 0.2wt% NaOH aqueous solution and the pretreatment solvent prepared in the step S1 are poured into a four-necked flask to be mixed, then stirred at 250rpm for 30min at room temperature, continuously stirred at room temperature for 10h at 200rpm, and then stirred at the same speed for 14h at 50 ℃ to obtain the OCA optical adhesive.
The preparation method of the modified OCA optical adhesive is the same as that of example 1.
Example 4
The preparation method of the three-layer acrylic optical adhesive is basically the same as that of example 1, except that: in the preparation method of the acrylic optical adhesive with the three-layer structure, the modified OCA optical adhesive is replaced by the OCA optical adhesive with the same amount.
The preparation method of the OCA optical adhesive is the same as that of example 1.
Comparative example 1
The preparation method of the three-layer acrylic optical adhesive is basically the same as that of example 4, except that: the preparation methods of the OCA optical adhesive are different.
The preparation method of the OCA optical adhesive comprises the following steps:
s1, adding 900g of water-soluble acrylic resin into a three-necked flask, then adding 1g of photoinitiator and 0.5g of tertiary dodecyl mercaptan, stirring and mixing for 3 hours at 25 ℃ by using a magnetic stirrer, wherein the stirring speed is 1200rpm, bubbling and degassing for 30 minutes by using nitrogen, and performing ultraviolet irradiation under a nitrogen atmosphere, wherein the irradiation power is 100W, and the irradiation time is 40 minutes to obtain an acrylic resin solvent;
s2, 13kg of 0.2wt% NaOH aqueous solution and the acrylic resin solvent prepared in the step S1 are poured into a four-necked flask, then stirred at 250rpm for 30min at room temperature, continuously stirred at room temperature for 10h at a stirring speed of 200rpm, and then stirred at the same speed for 14h at 50 ℃ to obtain OCA optical cement;
comparative example 2
The preparation method of the three-layer acrylic optical adhesive is basically the same as that of example 4, except that: the OCA optical adhesive was replaced with an equal amount of acrylic adhesive.
Test example 1
Thermal cracking performance test: reference is made to the test standard GB/T19466.1-2004 section 1 Plastic Differential Scanning Calorimetry (DSC) using a DSC scanner: general rule, the temperature is controlled to rise from normal temperature to 200 ℃, the temperature rising rate is 10 ℃/min, and the sample absorbs and releases heat in the scanning temperature rising process. The three-layer structured acrylic optical adhesives prepared in examples and comparative examples were placed in an aluminum crucible at a temperature rise rate of 10 ℃/min using DSC by taking 5mg, and the temperature rise was from 25 ℃ to 800 ℃ to analyze whether or not the adhesive had thermal weight loss during the entire temperature rise. The temperature at which thermal weight loss began and the mass residual percentage of the samples after 800 ℃ were recorded, and each sample was tested three times under the same conditions, and the final result was an average of three times. The test results are shown in Table 1.
Table 1: thermal cracking Performance test results
Test example 2
Adhesive strength test
And (3) adhesive strength test: the lapping mode of glass and glass is adopted, and two types of glass are adopted, wherein one type is 75mm multiplied by 25mm multiplied by 1mm, and the glass is used for manufacturing a sample wafer with parallel lapping strength; 0.008g of sample is weighed by using an analytical balance, dropping points are positioned at the formulated positions of the glass slides, two glass slides are attached, the formulated positions are circles, the diameter is controlled to be 6mm, the test is carried out by adopting a mode of stretching up and down at a constant speed, the traction rate is 2mm/min, and the temperature is controlled to be 25 ℃. Each sample was subjected to 3 trials and averaged. The test results are shown in Table 2.
Table 2: adhesive strength test results
Test example 3
Transmittance: the test is carried out according to the standard of GB/T14571.4-2008 "determination of ultraviolet transmittance of Industrial ethylene glycol" ultraviolet spectrophotometry, the method for testing the transmittance is that the acrylic optical cement prepared in the examples and comparative examples is uniformly coated between two pieces of optical glass with the thickness of 1mm, the two pieces of optical glass are clamped in the test process so as to avoid displacement, the test is carried out on the samples by a spectrophotometer, the temperature is 25 ℃, the thickness of a glue layer is 100um, each sample is subjected to 3 times of tests, and the average value is obtained. The test results are shown in Table 3.
Table 3: transmittance test results
| Test protocol | Transmittance/% |
| Example 1 | 94.31 |
| Example 2 | 93.24 |
| Example 3 | 93.10 |
| Example 4 | 92.51 |
| Comparative example 1 | 90.12 |
| Comparative example 2 | 90.67 |
From the test results, the thermal cracking performance, the bonding strength and the light transmittance of example 1 were all good, probably because the water-soluble acrylic resin and the hydroxyethyl acrylate were mixed and synthesized into a pretreatment solvent under the action of an initiator and a chain transfer agent, and then 3-propyl tri (trimethoxy silicon) methacrylate was grafted to obtain an OCA optical adhesive, which was further modified with polydimethyl diallyl amine chloride and compounded with isooctyl acrylate and glycidyl methacrylate to obtain a modified OCA optical adhesive, and the acrylic optical adhesive was prepared by coating. From the test results of table 1, it can be seen that the acrylic optical adhesive exhibits 2 stages of thermal weight loss, the first stage of thermal weight loss temperature being initiated at 79.5 c, because the reaction is promoted by adding a certain amount of NaOH aqueous solution and reaction solvent during the preparation of the acrylic optical adhesive by providing an alkaline reaction environment and reducing the optical adhesive, and thus the mass loss of the acrylic optical adhesive occurring at the initial stage of thermal decomposition is due to volatilization of the solvent. When the temperature reaches 391.7 ℃, the optical cement is decomposed secondarily, and at the moment, the main component acrylic resin in the optical cement is thermally cracked, and molecular chains are unfolded, so that adverse effects such as yellowing, atomization and the like are generated. The hydroxyethyl acrylate side chain consists of hydrophilic and hydrophobic segments, and is combined with water-soluble acrylic resin to form a simple linear entangled spiral structure due to high flexibility, polarity and chain length, so that free volume is reduced, a compact inter-chain structure is formed, and the entanglement of the chain structure and physical crosslinking formed by secondary bonding of the hydroxyethyl acrylate side chain inhibit the damage of the chain caused by heating, so that the thermal weight loss temperature is increased. The 3-methacrylic acid propyl tri (trimethoxy silicon) is fixed on the spiral structure through grafting and generates hydrogen bond interaction with silanol groups, so that the fluidity of the spiral chain is reduced, the cohesive strength of the material is increased, the stacking density is higher, and the thermal weightlessness temperature is further improved. The polydimethyl diallyl amine chloride is modified and is compounded with the isooctyl acrylate and the glycidyl methacrylate to form a semi-interpenetrating network structure, a heated damage mode is changed from cohesive damage to adhesive damage and then cohesive damage, the thermal weight loss temperature of the middle-layer modified OCA optical adhesive is improved, the synergistic effect of the mixed reactions enhances the thermal weight loss temperature of the acrylic optical adhesive, and the thermal stability is higher in the use process.
The physical crosslinking generated by entanglement and secondary bonding of the chain structure generates good cohesiveness, so that the adhesive strength is high, and the synthetic acrylic optical adhesive has lower modulus and larger contact area of materials. 3-propyl tris (trimethoxy silicon) methacrylate can improve bond strength by providing cohesive strength and energy dissipation; however, poor adhesion results from poor miscibility of isooctyl acrylate and glycidyl methacrylate with OCA optical cement. But due to the connection of the polydimethyl diallyl ammonium chloride, the miscibility of the OCA optical adhesive with the isooctyl acrylate and the glycidyl methacrylate is improved, so that the OCA optical adhesive has better bonding strength with the OCA optical adhesive.
The material adopted by the invention has better transparent property, the gaps among molecules are reduced by improving the miscibility, the light transmittance of the material is improved by modifying the OCA optical adhesive to form a semi-interpenetrating network structure, and the material is used as an intermediate layer for coating, so that the light transmittance of the whole acrylic optical adhesive can be improved, and the material is more suitable for photoelectric devices.
Claims (7)
1. A preparation method of an acrylic optical adhesive with a three-layer structure is characterized by comprising the following steps: the acrylic optical cement with the three-layer structure sequentially comprises an uppermost OCA optical cement film, a modified OCA optical cement film and a lowermost OCA optical cement film from top to bottom;
the lowest OCA optical adhesive film is obtained by coating OCA optical adhesive on a heavy release film;
the modified OCA optical adhesive film is obtained by coating a modified OCA optical adhesive on the lowest OCA optical adhesive film;
the uppermost OCA optical adhesive film is obtained by coating OCA optical adhesive on a modified OCA optical adhesive film;
the modified OCA optical adhesive is prepared by further modifying OCA optical adhesive;
the preparation method of the OCA optical adhesive comprises the following steps of:
s1, mixing 0.5-1.5 parts of water-soluble acrylic resin and 0.05-0.2 part of hydroxyethyl acrylate, then adding 0.0005-0.002 part of photoinitiator and 0.0003-0.001 part of chain transfer agent, stirring and mixing for 2-5 hours at 20-30 ℃ by using a magnetic stirrer, wherein the stirring speed is 1000-2000 rpm, bubbling nitrogen for degassing for 20-50 minutes, and performing ultraviolet curing under a nitrogen atmosphere to obtain a pretreatment solvent;
s2, mixing 10-15 parts of 0.1-0.3wt% NaOH aqueous solution and the pretreatment solvent prepared in the step S1, stirring at 200-500 rpm for 10-50 min at room temperature to obtain a reaction solution, adding 0.5-2 parts of 3-propyl tri (trimethoxy silicon) methacrylate into the reaction solution at the addition rate of 1-3 mL/min, firstly stirring at room temperature for 5-15 h at the stirring speed of 100-300 rpm, and then stirring at the same speed for 10-20 h at the temperature of 40-60 ℃ to obtain the OCA optical cement;
the preparation method of the modified OCA optical adhesive comprises the following steps of:
adding 0.2-0.6 part of polydimethyldiallyl ammonium chloride into a container, mixing 0.01-0.03 part of diisocyanate and 0.0003-0.001 part of dibutyltin dilaurate in a nitrogen atmosphere at 40-60 ℃, stirring for reacting for 30-50 min, then injecting 0.6-2 parts of OCA optical cement at the injection speed of 2-5 mL/min, stirring the reaction mixture for 30-50 min, and cooling to room temperature to obtain pretreated optical cement; adding 0.03-0.08 part of isooctyl acrylate and 0.02-0.05 part of glycidyl methacrylate into 0.5-2 parts of ethyl acetate to prepare a reaction mixture, adding the pretreatment optical cement into the reaction mixture, stirring for 30-50 min at 70-100 ℃ under nitrogen atmosphere, wherein the stirring speed is 200-500 rpm, dripping 0.005-0.02 part of free radical initiator into the reaction mixture in the stirring process, the dripping speed is 0.5-2 mL/min, reacting for 4-8 h, and cooling to room temperature to obtain the modified OCA optical cement.
2. The method for preparing the three-layer acrylic optical adhesive according to claim 1, comprising the steps of: uniformly coating OCA optical adhesive on a heavy release film, wherein the thickness is 20-40 mu m, ultraviolet curing to obtain a lowest OCA optical adhesive film, coating modified OCA optical adhesive on the lowest OCA optical adhesive film, coating the modified OCA optical adhesive film with the thickness of 30-50 mu m, ultraviolet curing to obtain a modified OCA optical adhesive film, coating OCA optical adhesive on the modified OCA optical adhesive film, coating the OCA optical adhesive with the thickness of 20-40 mu m, ultraviolet curing, coating the uppermost OCA optical adhesive film to obtain a three-layer structure composite adhesive, further curing the three-layer structure composite adhesive by adopting a thermal baking mode, and attaching a light release film on the cured OCA optical adhesive film to obtain the three-layer structure acrylic optical adhesive.
3. The method of claim 2, wherein: the temperature of the hot baking is 80-120 ℃ and the time is 5-15 min.
4. The method of claim 1, wherein: the chain transfer agent is tert-dodecyl mercaptan.
5. A method according to claim 1 or 2, characterized in that: the ultraviolet energy adopted by the ultraviolet curing is respectively and independently 200-1200 mJ/cm < 2 >.
6. The method of claim 1, wherein: the free radical initiator is prepared by dissolving 0.3-1 part by weight of azodiisobutyronitrile in 6-15 parts by weight of ethyl acetate.
7. An acrylic optical adhesive of three-layer structure, characterized by being prepared by the method of any one of claims 1 to 6.
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