CN115477900A - 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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- CN115477900A CN115477900A CN202211275526.1A CN202211275526A CN115477900A CN 115477900 A CN115477900 A CN 115477900A CN 202211275526 A CN202211275526 A CN 202211275526A CN 115477900 A CN115477900 A CN 115477900A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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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- C—CHEMISTRY; METALLURGY
- 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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- 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
- C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
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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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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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
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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 under the action of an initiator and a chain transfer agent to synthesize a pretreatment solvent, grafting 3-propyl tri (trimethoxy silicon) methacrylate to obtain the OCA optical adhesive, further modifying by adopting polydimethyl diallyl ammonium chloride, compounding with isooctyl acrylate and glycidyl methacrylate to obtain the 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 enhanced thermal decomposition performance, improved bonding strength, improved light transmittance, simple and environment-friendly preparation method, and suitability for being used as an adhesive of a photoelectric device.
Description
Technical Field
The invention relates to the technical field of optical cement, in particular to 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, is adhered to various adhered objects at room temperature in a short time, 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 is widely applied to the industrial field, such as optical transparent adhesives, packaging tapes, medical pads, masking tapes, protective films and hydrogels. However, general acrylics have various disadvantages such as low thermal stability and low adhesion strength to low surface energy substrates such as polyethylene, polypropylene and polydimethylsiloxane. A common solution is to treat the substrate surface with corona, plasma or chemical agents. However, surface treatment causes many problems such as substrate damage, waste disposal, and reduction in light transmittance. Therefore, it is important to develop an acrylic optical adhesive with good thermal stability, strong adhesion and high light transmittance.
The Chinese patent CN113755104A discloses a composite three-layer structure optical adhesive applied to a flexible folding screen, which sequentially comprises an SCA optical adhesive film, an elastic hybrid nano particle OCA optical adhesive film and an SCA optical adhesive film from top to bottom, wherein the SCA optical adhesive film is prepared by spraying an SCA hot melt adhesive on the surface of an adhered object through a hot melt adhesive pipe and a hot melt adhesive gun of a hot melt machine and then performing ultraviolet curing; the elastic hybrid nano particle OCA optical adhesive film is prepared by attaching elastic hybrid nano particles to the surface of an OCA optical adhesive film in a grafting mode, and reacting silicon dioxide nano particles with 3 (trimethoxysilyl) propyl methacrylate. According to the technical scheme, the nanometer particles are attached to the OCA optical adhesive film, and the two SCA optical adhesive films are covered on the upper surface and the lower surface of the OCA optical adhesive film, so that the probability of white spots of the SCA optical adhesive film during curing is greatly reduced. However, the optical adhesive with the three-layer structure prepared by the invention has poor thermal stability and low light transmittance.
Chinese patent No. CN108753182A discloses an OCA optical adhesive with excellent performance, which utilizes the compounding of acrylic acid-2-ethyl-1-dodecaester, phenoxybenzacrylic acid ester and N-vinylformamide to enable the high-temperature high-humidity monomer, high-folding monomer and adhesion promoting functional monomer to have efficient synergistic effect and show excellent compatibility and adaptability, and further adjusts other raw material components to have higher adaptability, so that the OCA optical adhesive can adopt a controllable activity polymerization method to carry out polymerization reaction, thereby obtaining the OCA optical adhesive with excellent performance, and effectively solving the technical problems of screen brightness and contrast reduction, visual effect deterioration and the like caused by poor high-temperature high-humidity resistance and wide molecular weight distribution of the traditional acrylic optical adhesive. However, the OCA optical cement prepared by the invention still has poor thermal stability and insufficient adhesive strength.
Disclosure of Invention
In view of the defects of poor thermal stability, weak adhesion and low light transmittance of the acrylic optical cement in the prior art, the invention aims to provide the acrylic optical cement with good thermal stability, strong adhesion and high light transmittance and the preparation method thereof.
In order to achieve the purpose of the invention, the 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 lowermost 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 the modified OCA optical adhesive on the lowermost 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 cement is prepared by further modifying the OCA optical cement.
The preparation method of the acrylic optical adhesive with the three-layer structure comprises the following steps:
uniformly coating the OCA optical cement on a heavy release film with the thickness of 20-40 mu m, carrying out ultraviolet curing to obtain a lowermost OCA optical cement film, coating the modified OCA optical cement on the lowermost OCA optical cement film with the coating thickness of 30-50 mu m, carrying out ultraviolet curing to obtain a modified OCA optical cement film, coating the modified OCA optical cement film with the coating thickness of 20-40 mu m, carrying out ultraviolet curing, wherein the coating layer is an uppermost OCA optical cement film, thus obtaining a three-layer structure composite cement, further carrying out curing treatment on the three-layer structure composite cement in a thermal baking mode, and pasting a light release film on the cured OCA optical cement film, thus obtaining the three-layer structure acrylic optical cement.
Preferably, the temperature of the thermal baking curing treatment is 80-120 ℃, and the time is 5-15 min.
Preferably, the preparation method of the OCA optical cement 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 the temperature of 20-30 ℃ by using a magnetic stirrer, wherein the stirring speed is 1000-2000 rpm, degassing for 20-50 min by using nitrogen bubbling, and performing ultraviolet curing in 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-methyl acrylic acid propyl tri (trimethoxy silicon) into the reaction solution at a rate of 1-3 mL/min, stirring at room temperature for 5-15 h at a stirring speed of 100-300 rpm, and stirring at the same speed at 40-60 ℃ for 10-20 h to obtain the OCA optical cement.
Preferably, the chain transfer agent is tert-dodecyl mercaptan.
Preferably, the ultraviolet energy used for ultraviolet curing is 200-1200 mJ/cm independently 2 。
The preparation method of the modified OCA optical adhesive comprises the following steps of:
adding 0.2-0.6 part of polydimethyldiallylamine chloride into a container, mixing 0.01-0.03 part of diisocyanate and 0.0003-0.001 part of dibutyltin dilaurate at the temperature of 40-60 ℃ in a nitrogen atmosphere, stirring for reaction for 30-50 min, 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 a 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 pretreated optical cement into the reaction mixture, stirring at the temperature of 70-100 ℃ for 30-50 min under the nitrogen atmosphere at the stirring speed of 200-500 rpm, dripping 0.005-0.02 part of free radical initiator into the reaction mixture during stirring at the dripping speed of 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 dibutyltin dilaurate.
Preferably, the free radical initiator is prepared by dissolving 0.3-1 part by weight of azobisisobutyronitrile in 6-15 parts by weight of ethyl acetate.
According to the invention, water-soluble acrylic resin and hydroxyethyl acrylate are mixed under the action of an initiator and a chain transfer agent to synthesize a pretreatment solvent, then 3-methyl propyl tri (trimethoxy silicon) acrylate is grafted to obtain OCA optical adhesive, poly dimethyl diallyl ammonium chloride is further adopted for modification, and the modified OCA optical adhesive is compounded with isooctyl acrylate and glycidyl methacrylate to obtain the modified OCA optical adhesive, and the acrylic optical adhesive is prepared by coating. The rise of the thermal weight loss temperature is caused by adding a certain amount of NaOH aqueous solution and reaction solvent in the preparation process of the acrylic optical cement, and the reaction is promoted by providing an alkaline reaction environment and reducing the viscosity of the optical cement, so that the quality loss of the acrylic optical cement in the initial stage of thermal decomposition is caused by the volatilization of the solvent. When the temperature continues to rise, the optical adhesive is decomposed for the second time, and at this time, the main component of the acrylic resin in the optical adhesive is thermally cracked, molecular chains are unfolded, and adverse effects such as yellowing and atomization 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 the free volume is reduced, a compact inter-chain structure is formed, and the chain is inhibited from being damaged by heating due to the entanglement of the chain structure and the physical crosslinking formed by secondary bonding of the hydroxyethyl acrylate side chain, and the thermal weight loss temperature is increased. 3-methyl acrylic 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 bulk density is higher, and the thermal weight loss temperature is further improved. The modified polydimethyl diallyl ammonium chloride, the isooctyl acrylate and the glycidyl methacrylate are compounded to form a semi-interpenetrating network structure, the heated failure mode is changed from cohesive failure to adhesive failure and then cohesive failure, the thermal weight loss temperature of the middle-layer modified OCA optical adhesive is increased, the thermal weight loss temperature of the acrylic optical adhesive is enhanced by the synergistic effect of the mixing reaction, and the acrylic optical adhesive has higher thermal stability in the using process.
The acrylic optical adhesive has high bonding strength due to good cohesion caused by entanglement of chain structure and physical crosslinking generated by secondary bonding, and the synthesized acrylic optical adhesive has lower modulus and larger contact area with materials. 3-propyl tris (trimethoxy silicon) methacrylate can improve the adhesive strength by providing cohesive strength and energy dissipation; however, the poor miscibility of isooctyl acrylate and glycidyl methacrylate with OCA optical cement results in poor adhesion. But due to the connection of the polydimethyldiallylamine 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.
The material adopted by the invention has better transparency, the intermolecular gap is reduced by improving the miscibility, the light transmittance of the material is improved by forming a semi-interpenetrating network structure through modifying the OCA optical cement, and the material is coated as an intermediate layer, so that the light transmittance of the whole acrylic optical cement 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 under the action of an initiator and a chain transfer agent to synthesize a pretreatment solvent, then 3-methyl propyl tri (trimethoxy silicon) acrylate is grafted to obtain the OCA optical adhesive, poly dimethyl diallyl ammonium chloride is further adopted for modification, and the modified OCA optical adhesive is compounded with isooctyl acrylate and glycidyl methacrylate to obtain the modified OCA optical adhesive, and the acrylic optical adhesive is prepared by 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 cement and the modified OCA optical cement to prepare the acrylic optical cement with a three-layer structure, the preparation method is simple and environment-friendly, the material distribution is reasonable, and the acrylic optical cement is suitable for being used as an adhesive of a photoelectric device.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
The parameters of part of the raw materials in the embodiment of the invention are as follows:
water-soluble acrylic resin, new materials of foshan city ltd, model: JT-207A, the content is more than or equal to 55 percent;
photoinitiator, chongqing new materials Co., ltd, model number: 184D, cargo number: AL-620474610153, the content of effective substances is as follows: 99.9 percent;
diisocyanate, shanghai North-China chemical science and technology Co., ltd, type: aqueous IPDI;
polydimethyldiallylchloride, warhamamek biomedical technologies, inc, cat #: whkmk-8695432, content of effective substances: 40%, CAS:26062-79-3;
heavy release film, huizhou Huaxiandao science and technology Limited, materials: BOPET, thickness: 38 um-150 um, type transparent film, release force: 25-30 g;
light release film, fraxinfeng composite limited, guan city, cat number: WFM0025, material: PET film, thickness: 0.025mm;
acrylic adhesives, shanghai sendai industries ltd, type: 349, viscosity: 13500Pa · s.
Example 1
An acrylic optical adhesive with a three-layer structure is prepared by the following steps:
uniformly coating OCA optical cement on heavy release film with thickness of 30 μm by coating machine, and ultraviolet curing with ultraviolet energy of 800mJ/cm 2 Coating the modified OCA optical adhesive on the bottom OCA optical adhesive film with a coating thickness of 40 μm, and performing ultraviolet curing with ultraviolet energy of 800mJ/cm 2 Obtaining a modified OCA optical adhesive film, coating OCA optical adhesive on the modified OCA optical adhesive film, wherein the coating thickness is 30 mu m, and the coating is cured by ultraviolet and the ultraviolet energy is 800mJ/cm 2 And the coating layer is the uppermost OCA optical adhesive film to obtain the three-layer structure composite adhesive, the three-layer structure composite adhesive is further cured by adopting a hot baking mode, the temperature of the hot baking curing process is 100 ℃, the baking time is 10min, and the cured OCA optical adhesive film is attached with a light release film to obtain the three-layer structure acrylic optical adhesive.
The preparation method of the OCA optical cement comprises the following steps:
s1, mixing 900g of water-soluble acrylic resin and 100g of hydroxyethyl acrylateAdding ester into a three-neck flask, adding 1g of photoinitiator and 0.5g of tert-dodecyl mercaptan, stirring and mixing at 25 deg.C for 3h with a magnetic stirrer at 1200rpm, degassing by bubbling with nitrogen gas for 30min, and ultraviolet curing under nitrogen atmosphere with ultraviolet energy of 400mJ/cm 2 Obtaining a pretreatment solvent;
s2, pouring 13kg of 0.2wt% NaOH aqueous solution and the pretreatment solvent prepared in step S1 into a four-necked flask for mixing, then stirring at 250rpm for 30min at room temperature, then adding 1kg of 3-propyltris (trimethoxy silicon) methacrylate into the four-necked flask at an addition rate of 2mL/min, first stirring at 200rpm for 10h at room temperature, and then stirring at 50 ℃ for 14h at the same speed to obtain an OCA optical cement.
The preparation method of the modified OCA optical cement comprises the following steps:
adding 400g of polydimethydiallylamine chloride into a two-neck flask, mixing 20g of diisocyanate and 0.5g of dibutyltin dilaurate at 50 ℃ in a nitrogen atmosphere, stirring for reacting for 40min, injecting 1kg of OCA optical cement at the injection speed of 3mL/min, stirring for 40min, and cooling to room temperature to obtain a pre-treatment optical cement; adding 65g of isooctyl acrylate and 35g of glycidyl methacrylate into 1kg of ethyl acetate to prepare a reaction mixture, adding the pretreated optical cement into the reaction mixture, stirring at the stirring speed of 300rpm for 40min at the temperature of 80 ℃ under the nitrogen atmosphere, dripping a free radical initiator prepared by dissolving 0.5g of azobisisobutyronitrile into 9.5g of ethyl acetate during stirring at the dripping speed of 1mL/min into the reaction mixture, reacting for 6h, and cooling to room temperature to obtain the modified OCA optical cement.
Example 2
An acrylic optical adhesive having a three-layer structure was prepared in substantially the same manner as in example 1, except that: the preparation methods of the OCA optical cement are different.
The preparation method of the OCA optical cement comprises the following steps:
s1, adding 900g of water-soluble acrylic resin into a three-neck flask, then adding 1g of photoinitiator and 0.5g of tert-dodecyl mercaptan, and stirring and mixing for 3 hours at 25 ℃ by using a magnetic stirrer at the stirring speed of1200rpm, degassing with nitrogen bubbling for 30min, and ultraviolet curing under nitrogen atmosphere with ultraviolet energy of 400mJ/cm 2 Obtaining an acrylic resin solvent;
s2, pouring 13kg of a 0.2wt% NaOH aqueous solution and the acrylic resin solvent prepared in step S1 into a four-necked flask for mixing, followed by stirring at 250rpm for 30min at room temperature, and then adding 1kg of 3-propyltris (trimethoxy silicon) methacrylate into the four-necked flask at a rate of 2mL/min, followed by stirring at 200rpm at room temperature for 10h, and then at 50 ℃ for 14h at the same rate, to obtain an OCA optical adhesive.
The preparation method of the modified OCA optical cement is the same as that of the example 1.
Example 3
An acrylic optical adhesive having a three-layer structure was prepared in substantially the same manner as in example 1, except that: the preparation methods of the OCA optical cement are different.
The preparation method of the OCA optical cement comprises the following steps:
s1, adding 900g of water-soluble acrylic resin and 100g of hydroxyethyl acrylate into a three-neck flask, then adding 1g of photoinitiator and 0.5g of tert-dodecyl mercaptan, stirring and mixing for 3h at 25 ℃ by using a magnetic stirrer, wherein the stirring speed is 1200rpm, bubbling and degassing by using nitrogen for 30min, and carrying out ultraviolet curing under a nitrogen atmosphere, wherein the ultraviolet energy is 400mJ/cm 2 Obtaining a pretreatment solvent;
s2, pouring 13kg of 0.2wt% NaOH aqueous solution and the pretreatment solvent prepared in step S1 into a four-necked flask for mixing, followed by stirring at 250rpm for 30min at room temperature, continuing stirring at room temperature for 10h at a stirring speed of 200rpm, and then stirring at the same speed for 14h at 50 ℃ to obtain an OCA optical cement.
The preparation method of the modified OCA optical cement is the same as that of the example 1.
Example 4
An acrylic optical adhesive having a three-layer structure was prepared in substantially the same manner as in 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 same amount of OCA optical adhesive.
The preparation method of the OCA optical cement is the same as that of the OCA optical cement in example 1.
Comparative example 1
An acrylic optical adhesive having a three-layer structure was prepared in substantially the same manner as in example 4, except that: the preparation methods of the OCA optical cement are different.
The preparation method of the OCA optical cement comprises the following steps:
s1, adding 900g of water-soluble acrylic resin into a three-neck flask, then adding 1g of photoinitiator and 0.5g of tert-dodecyl mercaptan, stirring and mixing for 3h at 25 ℃ by using a magnetic stirrer, wherein the stirring speed is 1200rpm, bubbling and degassing by using nitrogen for 30min, and carrying out ultraviolet irradiation under the nitrogen atmosphere, wherein the irradiation power is 100W, and the irradiation time is 40min to obtain an acrylic resin solvent;
s2, pouring 13kg of 0.2wt% NaOH aqueous solution and the acrylic resin solvent prepared in the step S1 into a four-neck flask, then stirring at 250rpm for 30min at room temperature, continuing stirring at room temperature for 10h, wherein the stirring speed is 200rpm, and then stirring at the same speed at 50 ℃ for 14h to obtain an OCA optical cement;
comparative example 2
An acrylic optical adhesive having a three-layer structure was prepared in substantially the same manner as in example 4, except that: the OCA optical cement was replaced with an equivalent amount of acrylic adhesive.
Test example 1
And (3) testing thermal cracking performance: using a DSC scanner, reference test standard GB/T19466.1-2004 "plastic Differential Scanning Calorimetry (DSC) part 1: general rules, the temperature is controlled to rise from normal temperature to 200 ℃, the temperature rise rate is 10 ℃/minute, and the sample absorbs and releases heat in the scanning temperature rise process. 5mg of the three-layer acrylic optical adhesive prepared in the examples and the comparative examples is put into an aluminum crucible, thermal performance analysis is carried out by DSC, the heating rate is 10 ℃/min, the temperature is increased from 25 ℃ to 800 ℃, and whether thermal weight loss occurs in the adhesive in the whole heating process is analyzed. The temperature at which the thermal weight loss starts and the mass residual percentage of the sample after 800 ℃ are recorded, each sample is tested three times under the same conditions, and the final result is the average value of the three times. The test results are shown in Table 1.
Table 1: results of thermal cracking Performance test
Test example 2
Adhesion Strength test
Testing the bonding strength: the lapping method of glass and glass is adopted, the specifications of the glass are two, one is 75mm multiplied by 25mm multiplied by 1mm, and the glass is used for manufacturing sample wafers with parallel lapping strength; weighing 0.008g of sample by using an analytical balance, dripping the sample to a formulated position of the glass slide, laminating the two glass slides, controlling the formulated position to be a circle and the diameter to be 6mm, testing by adopting a vertical uniform stretching mode, controlling the traction rate to be 2mm/min and controlling the temperature to be 25 ℃. Each sample was tested 3 times and the average was taken. The test results are shown in table 2.
Table 2: results of adhesion Strength test
Test example 3
Light transmittance: the test is carried out according to the GB/T14571.4-2008 ultraviolet spectrophotometry for measuring industrial ethylene glycol ultraviolet light transmittance, the light transmittance test method is that the acrylic optical cement prepared in the examples and the comparative examples is uniformly coated between two pieces of optical glass with the thickness of 1mm, the two pieces of optical glass are tightly added in the test process so as to avoid displacement, a sample is tested by a spectrophotometer, the temperature is 25 ℃, the thickness of a glue layer is 100 mu m, each sample is tested for 3 times, and the average value is obtained. The test results are shown in table 3.
Table 3: light 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, it can be seen that the thermal cracking performance, the bonding strength and the light transmittance of example 1 are all better, probably because the invention mixes the water-soluble acrylic resin and the hydroxyethyl acrylate under the action of the initiator and the chain transfer agent to synthesize the pretreatment solvent, then obtains the OCA optical adhesive by grafting 3-propyl tris (trimethoxy silicon) methacrylate, further adopts the polydimethyl diallyl ammonium chloride for modification, and compounds with isooctyl acrylate and glycidyl methacrylate to obtain the modified OCA optical adhesive, and obtains the acrylic optical adhesive by coating. From the test results in table 1, it can be seen that the acrylic optical adhesive has 2 thermal weight loss stages, and the first thermal weight loss temperature is at 79.5 ℃, because the reaction is promoted by adding a certain amount of NaOH aqueous solution and reaction solvent during the preparation process of the acrylic optical adhesive by providing an alkaline reaction environment and reducing the viscosity of the optical adhesive, and therefore the mass loss of the acrylic optical adhesive at the thermal decomposition starting stage is due to the volatilization of the solvent. When the temperature reaches 391.7 ℃, the optical adhesive is decomposed for the second time, and the main component of the acrylic resin in the optical adhesive 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 the free volume is reduced, a compact inter-chain structure is formed, and the chain is inhibited from being damaged by heating due to the entanglement of the chain structure and the physical crosslinking formed by secondary bonding of the hydroxyethyl acrylate side chain, and the thermal weight loss temperature is increased. 3-methyl acrylic 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 bulk density is higher, and the thermal weight loss temperature is further improved. The modified polydimethyl diallyl ammonium chloride, the isooctyl acrylate and the glycidyl methacrylate are compounded to form a semi-interpenetrating network structure, the heated failure mode is changed from cohesive failure to adhesive failure and then cohesive failure, the thermal weight loss temperature of the middle-layer modified OCA optical adhesive is increased, the thermal weight loss temperature of the acrylic optical adhesive is enhanced by the synergistic effect of the mixing reaction, and the acrylic optical adhesive has higher thermal stability in the using process.
The acrylic optical adhesive has high adhesive strength due to good cohesion caused by physical crosslinking through entanglement of the chain structure and secondary bonding, and the resultant acrylic optical adhesive has a lower modulus and a larger contact area with the material. 3-propyl tris (trimethoxy silicon) methacrylate can improve the adhesive strength by providing cohesive strength and energy dissipation; however, due to poor miscibility of isooctyl acrylate and glycidyl methacrylate with OCA optical cement, poor adhesion properties result. But due to the connection of the polydimethyldiallylamine 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.
The material adopted by the invention has better transparency, the intermolecular gap is reduced by improving the miscibility, the light transmittance of the material is improved by forming a semi-interpenetrating network structure through modifying the OCA optical cement, and the material is coated as an intermediate layer, so that the light transmittance of the whole acrylic optical cement can be improved, and the material is more suitable for photoelectric devices.
Claims (9)
1. An acrylic acid optical cement with a three-layer structure is characterized in that: the top OCA optical adhesive film, the modified OCA optical adhesive film and the bottom OCA optical adhesive film are sequentially arranged from top to bottom;
the lowermost 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 the modified OCA optical adhesive on the lowermost 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 cement is prepared by further modifying the OCA optical cement.
2. A method of making the three-layer acrylic optical adhesive of claim 1, comprising the steps of: uniformly coating the OCA optical cement on a heavy release film with the thickness of 20-40 mu m, carrying out ultraviolet curing to obtain a lowermost OCA optical cement film, coating the modified OCA optical cement on the lowermost OCA optical cement film with the coating thickness of 30-50 mu m, carrying out ultraviolet curing to obtain a modified OCA optical cement film, coating the modified OCA optical cement film with the coating thickness of 20-40 mu m, carrying out ultraviolet curing, wherein the coating layer is an uppermost OCA optical cement film, thus obtaining a three-layer structure composite cement, further carrying out curing treatment on the three-layer structure composite cement in a thermal baking mode, and attaching a light release film on the cured OCA optical cement film, thus obtaining the three-layer structure acrylic optical cement.
3. The method of claim 2, wherein: the temperature of the thermal baking is 80-120 ℃, and the time is 5-15 min.
4. The method of claim 2, wherein the OCA optical cement is prepared by the following steps in parts by weight:
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 and degassing by using nitrogen for 20-50 minutes, and carrying out ultraviolet curing in a nitrogen atmosphere to obtain a pretreatment solvent;
s2, mixing 10-15 parts of 0.1-0.3 wt% NaOH aqueous solution with 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-methyl acrylic acid propyl tris (trimethoxy silicon) into the reaction solution at a rate of 1-3 mL/min, stirring at room temperature for 5-15 h at a stirring speed of 100-300 rpm, and stirring at the same speed at 40-60 ℃ for 10-20 h to obtain the OCA optical cement.
5. The method of claim 4, wherein: the chain transfer agent is tertiary dodecyl mercaptan.
6. The method of claim 2 or 4, wherein: the ultraviolet energy adopted by the ultraviolet curing is 200-1200 mJ/cm independently 2 。
7. The method of claim 2, wherein the modified OCA optical cement is prepared by the following steps in parts by weight:
adding 0.2-0.6 part of polydimethyldiallylamine chloride into a container, mixing 0.01-0.03 part of diisocyanate and 0.0003-0.001 part of dibutyltin dilaurate at the temperature of 40-60 ℃ in a nitrogen atmosphere, stirring for reaction for 30-50 min, 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 a 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 pretreated optical cement into the reaction mixture, stirring at the temperature of 70-100 ℃ for 30-50 min under the nitrogen atmosphere at the stirring speed of 200-500 rpm, dripping 0.005-0.02 part of free radical initiator into the reaction mixture during stirring at the dripping speed of 0.5-2 mL/min, reacting for 4-8 h, and cooling to room temperature to obtain the modified OCA optical cement.
8. The method of claim 7, wherein: the catalyst is dibutyltin dilaurate.
9. The method of claim 7, wherein: the free radical initiator is prepared by dissolving 0.3-1 weight part of azodiisobutyronitrile in 6-15 weight parts of ethyl acetate.
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