CN115404020B - Acrylic optical adhesive film with three-layer structure for full-lamination and flexible folding screen and preparation method thereof - Google Patents
Acrylic optical adhesive film with three-layer structure for full-lamination and flexible folding screen and preparation method thereof Download PDFInfo
- Publication number
- CN115404020B CN115404020B CN202211262331.3A CN202211262331A CN115404020B CN 115404020 B CN115404020 B CN 115404020B CN 202211262331 A CN202211262331 A CN 202211262331A CN 115404020 B CN115404020 B CN 115404020B
- Authority
- CN
- China
- Prior art keywords
- acrylic
- reaction
- optical adhesive
- oca
- layer structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/6438—Polyimides or polyesterimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
-
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an acrylic optical adhesive film with a three-layer structure for a fully-attached and flexible folding screen and a preparation method thereof. The invention does not use solvent to assist polymerization, has the characteristics of high reaction conversion rate, low environmental pollution, high curing speed and simple process, overcomes the adverse effect caused by residual solvent and unreacted monomers, and is beneficial to maintaining the high light transmittance and the restorability of the product.
Description
Technical Field
The invention relates to the technical field of application of adhesive materials, in particular to an acrylic optical adhesive film with a three-layer structure for full lamination and a flexible folding screen and a preparation method thereof.
Background
With the large-scale application of flexible displays, optically Clear Adhesives (OCAs) made of acrylic resins have been widely used in the production of folded display screens. The optical adhesive needs to be resistant to high-ring measurement, high in transmittance and resistant to bending, and has no crease or no color difference after long-time bending. The existing OCA optical adhesive has the problem of low elasticity, and various defects are easy to generate under the action of external stress. The OCA optical adhesive needs to have high restorability and further to be able to restore to the original state when stress is removed. However, it is difficult for conventional optical adhesives to sufficiently release the applied stresses, and these residual stresses may cause defects in the assembled display, such as stress corrosion, delamination, cracking, and fatigue, resulting in a reduced lifetime.
Improving the performance of acrylic optical adhesives by modifying them is a viable solution. Chinese patent CN107236496a discloses a rosin-modified polyurethane acrylic low-shrinkage liquid optical adhesive and a preparation method thereof, and the specific preparation method is as follows: extracting rosin resin from Pinaceae plants, uniformly mixing the rosin resin with acrylic acid, acrylic acid alkyl ester and acrylamide, adding water, acetone, an emulsifying agent and an initiator into a reaction kettle, heating and uniformly stirring, cooling to room temperature, and regulating the pH value to be slightly alkaline to obtain a rosin modified acrylic acid prepolymer; and (3) uniformly stirring and mixing the rosin modified acrylic acid prepolymer, polyurethane acrylic resin, isobornyl methacrylate and spiro orthomonoacid ester expansion monomer, adding a photoinitiator, a coupling agent and a plasticizer, stirring, and removing bubbles to obtain the rosin modified polyurethane acrylic low-shrinkage liquid optical adhesive. The liquid optical adhesive prepared by the invention utilizes rosin to modify acrylic acid prepolymer, and combines spiro orthomonoacid ester expansion monomer to improve the problem of solidification shrinkage of the liquid optical adhesive. However, the invention adopts a solvent polymerization mode, the reaction conversion rate is low, and residual monomers can exist in the finished product; in addition, in the process of curing and film forming, water and acetone are difficult to be effectively removed, solvent molecules remained in the adhesive film or on the surface of the adhesive film are unfavorable for ensuring the full-lamination performance of the optical adhesive, and the structural defects caused by the solvent molecules also can reduce the light transmission performance of the optical adhesive, so that the solvent molecules are unfavorable for large-scale application in the field.
The photo-curing has the characteristics of high reaction conversion rate and no solvent in the curing process. Chinese patent CN104004489a provides a preparation method of anti-yellowing liquid optical adhesive, which uses epoxy acrylate resin, aliphatic polyurethane acrylate resin, aromatic polyurethane acrylate resin to match with each other and is assisted by monofunctional reactive diluent with low volume shrinkage, so as to prepare the liquid optical adhesive with high refraction, high light transmittance (> 99%), no yellowing due to wet heat, ultra-low hardness (shore E2-10) and low volume shrinkage. The patent uses aromatic polyurethane acrylate resin, however, in the internal structure of the aromatic polymer material, there may be strong intramolecular or intermolecular charge transfer interaction, and a charge transfer complex is easily formed between an electron donor and an electron acceptor, and in this process, the optical adhesive has significant absorption to visible light due to charge transition and transfer, so that the color and light transmittance of the optical adhesive are deteriorated.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides an acrylic optical film with full-lamination and excellent flexibility and a method for preparing the same.
The invention prepares and uses an acrylic resin, wherein 2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride and 3- (aminomethyl) hex-1-ol are taken as initial raw materials, and are combined through imidization reaction, and then undergo nucleophilic addition reaction with L-lysine diisocyanate, and the obtained product is polymerized with 2-acrylic acid-4-hydroxypropyl ester to obtain an oligomer. The acrylic resin is obtained by mixing the oligomer with isobornyl acrylate and ethoxyethoxy ethyl acrylate according to a proportion. The acrylic OCA optical adhesive prepared from the acrylic resin is crosslinked in the light curing process, and the formed optical adhesive film has good adhesive force to OCA layers on two sides, has strong restorability and meets the use requirement of the flexible folding screen.
According to the invention, the acrylic OCA optical adhesive prepared from the acrylic resin is combined with the traditional OCA optical adhesive to form a three-layer structure, the upper and lower OCA adhesives are soft, the elastic modulus is low, foam discharging is facilitated, the level difference filling rate is high, the middle acrylic OCA optical adhesive layer is hard, the whole elasticity of the adhesive is increased while die cutting is facilitated between the two adhesives, and the whole adhesive is convenient for tearing and reworking.
The preparation method of the acrylic optical adhesive film with the three-layer structure for the full-lamination and flexible folding screen comprises the following steps:
s1, uniformly mixing acrylic resin with a cross-linking agent and a photoinitiator to obtain acrylic OCA optical cement for later use;
s2, coating OCA optical adhesive on one surface of the release film by adopting an automatic coating device, and obtaining a first OCA adhesive layer after ultraviolet curing; coating the acrylic OCA optical adhesive on the first OCA adhesive layer, and obtaining a second OCA adhesive layer after ultraviolet curing; coating OCA optical adhesive on the second OCA adhesive layer, attaching a release film, and curing by ultraviolet light to obtain a third OCA adhesive layer; the optical adhesive film with the three-layer OCA adhesive layer structure is the acrylic optical adhesive film with the three-layer structure for the full-lamination and flexible folding screen.
Preferably, the ratio of the components of the acrylic OCA optical adhesive in step S1 is: 0.3 to 1.5 weight percent of cross-linking agent, 0.5 to 3.5 weight percent of photoinitiator and the balance of acrylic resin.
The acrylic acid oligomer prepared by the invention contains a fluorinated aromatic imine structure and a flexible long methylene chain, and has good compatibility with an interface layer and high adhesive force during coating. Since the resin exhibits hydrophobicity as a whole, moisture existing in the environment is less remained at the interface when cured, and defects of the optical adhesive film are reduced, and excellent optical performance is exhibited.
The aromatic imine structure in the molecular chain of the acrylic acid oligomer has certain rigidity, and the mechanical property of the optical adhesive film can be enhanced after the curing. The ether-oxygen bond structure of the ethoxyethoxy ethyl acrylate gives the product good flexibility and recovery, and the long-chain structure can overcome the steric hindrance of the functional group of the acrylic oligomer, and can be better combined with the base film during curing. Fluorinated isopropenyl groups increase the free volume of the molecule, inhibiting the formation of intermolecular or intramolecular charge transfer; the group has strong polarity, so that the charges are difficult to move, and the phenomenon that the color and the light transmittance of the material are deteriorated due to the transition and the transfer of the charges is greatly relieved.
Preferably, the acrylic resin is prepared by the following steps in parts by weight:
under the anaerobic condition, 19.0 to 25.0 parts of 2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, 13.8 to 18.0 parts of 3- (aminomethyl) hex-1-ol and 200 to 275 parts of N, N-dimethylformamide are uniformly mixed to obtain a reaction mixed solution; continuously adding 35-45 parts of toluene into the reaction mixed solution, uniformly mixing, heating and carrying out imidization reaction; removing toluene through distillation after imidization reaction is finished, pouring a reaction product into water at 0-4 ℃, filtering and collecting a filter cake, washing the filter cake until an eluate is neutral, and then drying to obtain an imidization product for later use;
under the anaerobic condition, 17.4 to 22.6 parts of imidization product is dissolved in 15 to 25 parts of acetone, 11.8 to 15.3 parts of L-lysine diisocyanate is continuously added into the solution, 0.1 to 0.2 part of dibutyltin dilaurate is continuously added after uniform stirring, and nucleophilic addition reaction is carried out by heating under the catalysis of dibutyltin dilaurate; obtaining a polymerization reaction stock solution after the nucleophilic addition reaction is finished for standby;
m3, under the anaerobic condition, continuously adding 7.5-10.0 parts of 2-acrylic acid-4-hydroxypropyl ester into the polymerization reaction stock solution, uniformly mixing and carrying out polymerization reaction; pouring the reaction product into water at 0-4 ℃ after the polymerization reaction is finished, filtering and collecting a filter cake, washing the filter cake until an eluate is neutral, and then drying to obtain an acrylic acid oligomer for later use;
and M4, mixing the acrylic oligomer, the ethoxyethoxy ethyl acrylate and the isobornyl acrylate according to a proportion until all components are uniform, and obtaining the acrylic resin.
It is further preferable that the imidization reaction in the step M1 is carried out at a reaction temperature of 115 to 130℃for a reaction time of 4 to 10 hours.
Further preferably, the reaction temperature of the nucleophilic addition reaction in the step M2 is 30 to 50 ℃ and the reaction time is 0.5 to 3 hours.
It is further preferred that the polymerization reaction in step M3 is carried out at a reaction temperature of 25 to 35℃for a reaction time of 1.5 to 4 hours.
Further preferably, in the step M4, the mass ratio of the acrylic oligomer, the ethoxyethoxyethyl acrylate, and the isobornyl acrylate in the acrylic resin is 12 to 19: 8-20: 11.
preferably, the cross-linking agent in the step S1 is any one of ethylene glycol dimethacrylate, 1, 4-butanediol diacrylate, diethylene glycol diacrylate, allyl methacrylate, 1, 6-hexanediol diacrylate and ethylene glycol diacrylate.
Preferably, the UV-light irradiation amount of the photo-curing in step S2 is 2100 to 4000mJ/cm 2 The curing time is 5-15 min independently.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the invention.
The invention has the following description and functions of partial raw materials in the formula:
isobornyl acrylate: organic matter with molecular formula of C 13 H 20 O 2 . The modified polyurethane adhesive is applied to adhesives and special coatings, and has high activity, high hardness and low shrinkage. The IBOA is used as an active diluent for the radiation curing coating, so that the viscosity of the coating can be effectively reduced, the workability is improved, and the leveling property of the coating is improved.
Ethoxyethoxyethyl acrylate: the organic matter is colorless or yellow transparent liquid, is applied to ink, wood, plastic, paper coating and solder resist ink, and has the characteristics of low shrinkage, good flexibility and excellent dilutability.
The invention has the beneficial effects that:
compared with the prior art, the acrylic OCA optical adhesive prepared from acrylic resin is combined with the traditional OCA optical adhesive to form a three-layer structure, the upper layer of OCA adhesive and the lower layer of OCA adhesive are soft, the elastic modulus is low, foam discharging is facilitated, the level difference filling rate is high, the middle acrylic OCA optical adhesive layer is hard, the die cutting is facilitated between the two layers of adhesive, the overall elasticity of the adhesive is increased, and the whole adhesive is favorable for being torn up and reworked.
Compared with the prior art, the invention takes 2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, 3- (aminomethyl) hex-1-ol, L-lysine diisocyanate and 2-acrylic acid-4-hydroxypropyl ester as raw materials to prepare an oligomer. The invention mixes the oligomer with isobornyl acrylate and ethoxyethoxy ethyl acrylate according to a proportion to obtain a novel acrylic resin. The inside of the optical adhesive film formed by photo-curing has good adhesive force and strong restorability, and the optical adhesive film can not be layered after being folded for many times, thereby meeting the use requirement of the flexible folding screen.
Compared with the prior art, the acrylic resin provided by the invention has a fluorinated aromatic imine structure and a flexible long methylene chain, and has good compatibility with an interface layer and high adhesive force during coating. Fluorinated isopropenyl groups increase the free volume of the molecule, inhibiting the formation of intermolecular or intramolecular charge transfer; the group has strong polarity, so that the charges are difficult to move, and the phenomenon that the color and the light transmittance of the material are deteriorated due to the transition and the transfer of the charges is greatly relieved.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The comparative example and the examples of the present invention have the following parameters of part of raw materials:
release film, model: r502TE, thickness: 0.05mm, available from Shenzhen Ruihua coating technology Co., ltd;
the OCA optical cement is prepared by adopting the method described in the CN113249038A example 3;
2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, CAS number: 1107-00-2;
4,4' -oxydiphthalic anhydride, CAS no: 1823-59-2;
3- (aminomethyl) hexan-1-ol, CAS no: 1354953-13-1;
l-lysine diisocyanate, CAS number: 45172-15-4;
2-4-hydroxypropyl acrylate, CAS number: 2478-10-6;
isobornyl acrylate, CAS no: 5888-33-5;
ethoxyethoxyethyl acrylate, CAS number: 7328-17-8;
ethylene glycol diacrylate, CAS number: 2274-11-5;
photoinitiator, brand Ai Jianmeng IGM, model: omnirad 127D, available from new materials inc.
Example 1
An acrylic optical adhesive film with a three-layer structure for a full-lamination and flexible folding screen is prepared by the following method:
s1, uniformly mixing acrylic resin with ethylene glycol diacrylate and a photoinitiator to obtain acrylic OCA optical adhesive for later use;
s2, coating OCA optical adhesive on one surface of the release film by adopting an automatic coating device, and obtaining a first OCA adhesive layer after ultraviolet curing; coating the acrylic OCA optical adhesive on the first OCA adhesive layer, and obtaining a second OCA adhesive layer after ultraviolet curing; coating OCA optical adhesive on the second OCA adhesive layer, attaching a release film, and curing by ultraviolet light to obtain a third OCA adhesive layer; the optical adhesive film with the three-layer OCA adhesive layer structure is the acrylic optical adhesive film with the three-layer structure for the full-lamination and flexible folding screen.
The proportions of the components of the acrylic OCA optical adhesive in the step S1 are as follows: 1.5wt% of ethylene glycol diacrylate, 3.5wt% of photoinitiator and the balance of acrylic resin.
The coating weights of the coating in the step S2 are all 0.8g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Ultraviolet curing ultraviolet irradiation amounts are 3400mJ/cm 2 The curing time was 7min.
The preparation method of the acrylic resin comprises the following steps:
under the protection of M1 and nitrogen, 19.0kg of 2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, 13.8kg of 3- (aminomethyl) hex-1-ol and 200kg of N, N-dimethylformamide are uniformly mixed to obtain a reaction mixture; continuously adding 35kg of toluene into the reaction mixed solution, uniformly mixing, heating and carrying out imidization reaction, wherein the reaction temperature is 120 ℃, and the reaction time is 6 hours; removing toluene through distillation after imidization reaction is finished, pouring a reaction product into water at 4 ℃, filtering and collecting a filter cake, washing the filter cake until an eluate is neutral, and then drying to obtain an imidization product for later use;
under the protection of M2 and nitrogen, dissolving 17.4kg of imidization product in 15kg of acetone, continuously adding 11.8kg of L-lysine diisocyanate into the solution, uniformly stirring, continuously adding 0.1kg of dibutyltin dilaurate, heating under the catalysis of dibutyltin dilaurate, and carrying out nucleophilic addition reaction at 40 ℃ for 1.5h; obtaining a polymerization reaction stock solution after the nucleophilic addition reaction is finished for standby;
under the protection of M3 and nitrogen, continuously adding 7.5kg of 2-acrylic acid-4-hydroxypropyl ester into the polymerization reaction stock solution, uniformly mixing and carrying out polymerization reaction, wherein the reaction temperature is 30 ℃, and the reaction time is 3 hours; pouring the reaction product into water at 4 ℃ after the polymerization reaction is finished, filtering and collecting a filter cake, washing the filter cake until an eluate is neutral, and then drying to obtain an acrylic acid oligomer for later use;
m4, mixing the acrylic oligomer and the isobornyl acrylate according to a mass ratio of 19:11 are mixed until the components are uniform, and the acrylic resin is obtained.
Example 2
An acrylic optical adhesive film with a three-layer structure for a full-lamination and flexible folding screen is prepared by the following method:
s1, uniformly mixing acrylic resin with ethylene glycol diacrylate and a photoinitiator to obtain acrylic OCA optical adhesive for later use;
s2, coating OCA optical adhesive on one surface of the release film by adopting an automatic coating device, and obtaining a first OCA adhesive layer after ultraviolet curing; coating the acrylic OCA optical adhesive on the first OCA adhesive layer, and obtaining a second OCA adhesive layer after ultraviolet curing; coating OCA optical adhesive on the second OCA adhesive layer, attaching a release film, and curing by ultraviolet light to obtain a third OCA adhesive layer; the optical adhesive film with the three-layer OCA adhesive layer structure is the acrylic optical adhesive film with the three-layer structure for the full-lamination and flexible folding screen.
The proportions of the components of the acrylic OCA optical adhesive in the step S1 are as follows: 1.5wt% of ethylene glycol diacrylate, 3.5wt% of photoinitiator and the balance of acrylic resin.
The coating weights of the coating in the step S2 are all 0.8g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Ultraviolet curing ultraviolet irradiation amounts are 3400mJ/cm 2 The curing time was 7min.
The preparation method of the acrylic resin comprises the following steps:
under the protection of M1 and nitrogen, 19.0kg of 2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, 13.8kg of 3- (aminomethyl) hex-1-ol and 200kg of N, N-dimethylformamide are uniformly mixed to obtain a reaction mixture; continuously adding 35kg of toluene into the reaction mixed solution, uniformly mixing, heating and carrying out imidization reaction, wherein the reaction temperature is 120 ℃, and the reaction time is 6 hours; removing toluene through distillation after imidization reaction is finished, pouring a reaction product into water at 4 ℃, filtering and collecting a filter cake, washing the filter cake until an eluate is neutral, and then drying to obtain an imidization product for later use;
under the protection of M2 and nitrogen, dissolving 17.4kg of imidization product in 15kg of acetone, continuously adding 11.8kg of L-lysine diisocyanate into the solution, uniformly stirring, continuously adding 0.1kg of dibutyltin dilaurate, heating under the catalysis of dibutyltin dilaurate, and carrying out nucleophilic addition reaction at 40 ℃ for 1.5h; obtaining a polymerization reaction stock solution after the nucleophilic addition reaction is finished for standby;
under the protection of M3 and nitrogen, continuously adding 7.5kg of 2-acrylic acid-4-hydroxypropyl ester into the polymerization reaction stock solution, uniformly mixing and carrying out polymerization reaction, wherein the reaction temperature is 30 ℃, and the reaction time is 3 hours; pouring the reaction product into water at 4 ℃ after the polymerization reaction is finished, filtering and collecting a filter cake, washing the filter cake until an eluate is neutral, and then drying to obtain an acrylic acid oligomer for later use;
m4, mixing the acrylic oligomer and the ethoxyethoxyethyl acrylate according to a mass ratio of 19:20 are mixed until the components are uniform, and the acrylic resin is obtained.
Example 3
An acrylic optical adhesive film with a three-layer structure for a full-lamination and flexible folding screen is prepared by the following method:
s1, uniformly mixing acrylic resin with ethylene glycol diacrylate and a photoinitiator to obtain acrylic OCA optical adhesive for later use;
s2, coating OCA optical adhesive on one surface of the release film by adopting an automatic coating device, and obtaining a first OCA adhesive layer after ultraviolet curing; coating the acrylic OCA optical adhesive on the first OCA adhesive layer, and obtaining a second OCA adhesive layer after ultraviolet curing; coating OCA optical adhesive on the second OCA adhesive layer, attaching a release film, and curing by ultraviolet light to obtain a third OCA adhesive layer; the optical adhesive film with the three-layer OCA adhesive layer structure is the acrylic optical adhesive film with the three-layer structure for the full-lamination and flexible folding screen.
The proportions of the components of the acrylic OCA optical adhesive in the step S1 are as follows: 1.5wt% of ethylene glycol diacrylate, 3.5wt% of photoinitiator and the balance of acrylic resin.
The coating weights of the coating in the step S2 are all 0.8g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Ultraviolet curing ultraviolet irradiation amounts are 3400mJ/cm 2 The curing time was 7min.
The preparation method of the acrylic resin comprises the following steps:
under the protection of M1 and nitrogen, 19.0kg of 2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, 13.8kg of 3- (aminomethyl) hex-1-ol and 200kg of N, N-dimethylformamide are uniformly mixed to obtain a reaction mixture; continuously adding 35kg of toluene into the reaction mixed solution, uniformly mixing, heating and carrying out imidization reaction, wherein the reaction temperature is 120 ℃, and the reaction time is 6 hours; removing toluene through distillation after imidization reaction is finished, pouring a reaction product into water at 4 ℃, filtering and collecting a filter cake, washing the filter cake until an eluate is neutral, and then drying to obtain an imidization product for later use;
under the protection of M2 and nitrogen, dissolving 17.4kg of imidization product in 15kg of acetone, continuously adding 11.8kg of L-lysine diisocyanate into the solution, uniformly stirring, continuously adding 0.1kg of dibutyltin dilaurate, heating under the catalysis of dibutyltin dilaurate, and carrying out nucleophilic addition reaction at 40 ℃ for 1.5h; obtaining a polymerization reaction stock solution after the nucleophilic addition reaction is finished for standby;
under the protection of M3 and nitrogen, continuously adding 7.5kg of 2-acrylic acid-4-hydroxypropyl ester into the polymerization reaction stock solution, uniformly mixing and carrying out polymerization reaction, wherein the reaction temperature is 30 ℃, and the reaction time is 3 hours; pouring the reaction product into water at 4 ℃ after the polymerization reaction is finished, filtering and collecting a filter cake, washing the filter cake until an eluate is neutral, and then drying to obtain an acrylic acid oligomer for later use;
m4, mixing the acrylic oligomer, ethoxyethoxyethyl acrylate and isobornyl acrylate according to a mass ratio of 19:20:11 are mixed until the components are uniform, and the acrylic resin is obtained.
Example 4
An acrylic optical adhesive film with a three-layer structure for a full-lamination and flexible folding screen is prepared by the following method:
s1, uniformly mixing acrylic resin with ethylene glycol diacrylate and a photoinitiator to obtain acrylic OCA optical adhesive for later use;
s2, coating OCA optical adhesive on one surface of the release film by adopting an automatic coating device, and obtaining a first OCA adhesive layer after ultraviolet curing; coating the acrylic OCA optical adhesive on the first OCA adhesive layer, and obtaining a second OCA adhesive layer after ultraviolet curing; coating OCA optical adhesive on the second OCA adhesive layer, attaching a release film, and curing by ultraviolet light to obtain a third OCA adhesive layer; the optical adhesive film with the three-layer OCA adhesive layer structure is the acrylic optical adhesive film with the three-layer structure for the full-lamination and flexible folding screen.
The proportions of the components of the acrylic OCA optical adhesive in the step S1 are as follows: 1.5wt% of ethylene glycol diacrylate, 3.5wt% of photoinitiator and the balance of acrylic resin.
The coating weights of the coating in the step S2 are all 0.8g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Ultraviolet curing ultraviolet irradiation amounts are 3400mJ/cm 2 The curing time was 7min.
The preparation method of the acrylic resin comprises the following steps:
under the protection of M1 and nitrogen, 13.3kg of 4,4' -oxydiphthalic anhydride, 13.8kg of 3- (aminomethyl) hex-1-ol and 200kg of N, N-dimethylformamide are uniformly mixed to obtain a reaction mixed solution; continuously adding 35kg of toluene into the reaction mixed solution, uniformly mixing, heating and carrying out imidization reaction, wherein the reaction temperature is 120 ℃, and the reaction time is 6 hours; removing toluene through distillation after imidization reaction is finished, pouring a reaction product into water at 4 ℃, filtering and collecting a filter cake, washing the filter cake until an eluate is neutral, and then drying to obtain an imidization product for later use;
under the protection of M2 and nitrogen, dissolving 13.9kg of imidization product in 15kg of acetone, continuously adding 11.8kg of L-lysine diisocyanate into the solution, uniformly stirring, continuously adding 0.1kg of dibutyltin dilaurate, heating under the catalysis of dibutyltin dilaurate, and carrying out nucleophilic addition reaction at 40 ℃ for 1.5h; obtaining a polymerization reaction stock solution after the nucleophilic addition reaction is finished for standby;
under the protection of M3 and nitrogen, continuously adding 7.5kg of 2-acrylic acid-4-hydroxypropyl ester into the polymerization reaction stock solution, uniformly mixing and carrying out polymerization reaction, wherein the reaction temperature is 30 ℃, and the reaction time is 3 hours; pouring the reaction product into water at 4 ℃ after the polymerization reaction is finished, filtering and collecting a filter cake, washing the filter cake until an eluate is neutral, and then drying to obtain an acrylic acid oligomer for later use;
m4, mixing the acrylic oligomer, ethoxyethoxyethyl acrylate and isobornyl acrylate according to a mass ratio of 19:20:11 are mixed until the components are uniform, and the acrylic resin is obtained.
Comparative example 1
An acrylic optical adhesive film with a three-layer structure for a full-lamination and flexible folding screen is prepared by the following method:
s1, uniformly mixing acrylic resin with ethylene glycol diacrylate and a photoinitiator to obtain acrylic OCA optical adhesive for later use;
s2, coating OCA optical adhesive on one surface of the release film by adopting an automatic coating device, and obtaining a first OCA adhesive layer after ultraviolet curing; coating the acrylic OCA optical adhesive on the first OCA adhesive layer, and obtaining a second OCA adhesive layer after ultraviolet curing; coating OCA optical adhesive on the second OCA adhesive layer, attaching a release film, and curing by ultraviolet light to obtain a third OCA adhesive layer; the optical adhesive film with the three-layer OCA adhesive layer structure is the acrylic optical adhesive film with the three-layer structure for the full-lamination and flexible folding screen.
The proportions of the components of the acrylic OCA optical adhesive in the step S1 are as follows: 1.5wt% of ethylene glycol diacrylate, 3.5wt% of photoinitiator and the balance of acrylic resin.
The coating weights of the coating in the step S2 are all 0.8g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Ultraviolet curing ultraviolet irradiation amounts are 3400mJ/cm 2 The curing time was 7min.
The preparation method of the acrylic resin comprises the following steps:
ethoxy ethyl acrylate and isobornyl acrylate are mixed according to the mass ratio of 20:11 are mixed until the components are uniform, and the acrylic resin is obtained.
Test example 1
The light transmittance and haze test of the acrylic optical adhesive film prepared by the invention is carried out by referring to the specific method and steps in the national standard GB/T2410-2008 determination of light transmittance and haze of transparent plastics. The sample is a wafer with the diameter of 50mm, the surfaces of the two sides of the sample are flat and parallel, dust, greasy dirt, foreign matters, scratches and the like are avoided, and no visible internal defects and particles are generated. Three samples are prepared for each group, and a common test group is subjected to test after being adjusted for 48 hours according to the state of GB/T2918-2018 under the environment of 23 ℃ and relative humidity of 50%; after being vertically folded at 90 degrees for 500 times, the folding test group is subjected to test after being adjusted for 48 hours according to the state of GB/T2918-2018 under the environment of 23 ℃ and relative humidity of 50 percent. The test results were averaged mathematically as required and the surface morphology and delamination status of the folded test group samples were observed. The transmittance and haze test results of the acrylic optical film are shown in table 1, and the conditions of the folded samples are shown in table 2.
Table 1:
table 2:
| name of the name | Whether or not there is a crease | With or without delamination | Has no color difference |
| Example 1 | Has the following components | Without any means for | Has the following components |
| Example 2 | Without any means for | Without any means for | Has the following components |
| Example 3 | Without any means for | Without any means for | Without any means for |
| Example 4 | Has the following components | Has the following components | Has the following components |
| Comparative example 1 | Has the following components | Has the following components | Has the following components |
In the application in the field, the optical adhesive film should meet the technical indexes of light transmittance > 90% and haze < 1%; when applied to a display having a folding function, it is required to have characteristics of bending resistance, no crease after bending, no color difference, and no influence on light transmittance. From the test results of tables 1 and 2, it can be seen that example 3 has the best optical properties, and can maintain good light transmittance and low haze even after multiple folding. The result of this phenomenon may be that the fluorinated isopropenyl group increases the free volume of the molecule, inhibiting the formation of intermolecular or intramolecular charge transfer; the group has strong polarity, so that the charges are difficult to move, and the phenomenon that the color and the light transmittance of the material are deteriorated due to the transition and the transfer of the charges is greatly relieved.
Test example 2
The environmental suitability test of the acrylic optical adhesive film prepared by the invention is carried out by referring to the specific method and steps in the national standard GB/T26331-2010 optical film element environmental suitability test method. The test items are alternating damp-heat tests, the samples are placed under standard atmospheric conditions for 1 hour and then tested, the pretreated samples are placed in a test box under the standard atmospheric conditions, the temperature and the humidity in the test box are adjusted to reach the initial state of circulation, the test box is kept for 10 minutes and then starts to time, and then the temperature and the humidity are adjusted according to the temperature and the humidity requirements shown in the figure 2 in the section 4.5.2 of the standard. The test severity level was 02 and the number of cycles was 10. After the test is completed, the sample is directly taken out from the test box for recovery treatment, is rinsed for 5min by deionized water or steam room water, and is then shaken or dried by air flow to remove water drops. After the test, the state of the sample was evaluated according to the criteria of table 9 in section 5. The results of the environmental suitability test of the acrylic optical film are shown in table 3.
Table 3:
the sample state after the alternating wet heat test reflects the environmental suitability of the acrylic optical adhesive film, and it can be seen from the test results of table 3 that the environmental suitability of example 3 is optimal. The result of this phenomenon may be that the acrylic oligomer prepared in this example contains a fluorinated aromatic imine structure and a flexible long methylene chain, and the compatibility with the interface layer is good and the adhesion is high during coating; because the resin is integrally hydrophobic, when the resin is solidified, the residual of moisture existing in the environment at the interface is less, so that the defect of the optical adhesive film is reduced, the three-layer structure is tightly combined, and the adaptability under severe environment is stronger.
Claims (7)
1. The preparation method of the acrylic optical adhesive film with the three-layer structure for the full-lamination and flexible folding screen is characterized by comprising the following steps of:
s1, uniformly mixing acrylic resin with a cross-linking agent and a photoinitiator to obtain acrylic OCA optical cement for later use;
s2, coating OCA optical adhesive on one surface of the release film by adopting an automatic coating device, and obtaining a first OCA adhesive layer after ultraviolet curing; coating the acrylic OCA optical adhesive on the first OCA adhesive layer, and obtaining a second OCA adhesive layer after ultraviolet curing; coating OCA optical adhesive on the second OCA adhesive layer, attaching a release film, and curing by ultraviolet light to obtain a third OCA adhesive layer; the optical adhesive film with the three-layer OCA adhesive layer structure is the acrylic optical adhesive film with the three-layer structure for the full-lamination and flexible folding screen;
the proportions of the components of the acrylic OCA optical adhesive in the step S1 are as follows: 0.3-1.5wt% of cross-linking agent, 0.5-3.5wt% of photoinitiator and the balance of acrylic resin;
the preparation method of the acrylic resin comprises the following steps of:
under the anaerobic condition, uniformly mixing 19.0-25.0 parts of 2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, 13.8-18.0 parts of 3- (aminomethyl) hex-1-ol and 200-275 parts of N, N-dimethylformamide to obtain a reaction mixed solution; continuously adding 35-45 parts of toluene into the reaction mixed solution, uniformly mixing, heating and carrying out imidization reaction; removing toluene through distillation after imidization reaction is finished, pouring a reaction product into water at 0-4 ℃, filtering and collecting a filter cake, washing the filter cake until an eluate is neutral, and then drying to obtain an imidization product for later use;
under the anaerobic condition, dissolving 17.4-22.6 parts of the imidization product in 15-25 parts of acetone, continuously adding 11.8-15.3 parts of L-lysine diisocyanate into the solution, uniformly stirring, continuously adding 0.1-0.2 part of dibutyltin dilaurate, and heating under the catalysis of dibutyltin dilaurate to carry out nucleophilic addition reaction; obtaining a polymerization reaction stock solution after the nucleophilic addition reaction is finished for standby;
m3, continuously adding 7.5-10.0 parts of 2-acrylic acid-4-hydroxypropyl ester into the polymerization reaction stock solution under the anaerobic condition, uniformly mixing and carrying out polymerization reaction; pouring the reaction product into water at 0-4 ℃ after the polymerization reaction is finished, filtering and collecting a filter cake, washing the filter cake until an eluate is neutral, and then drying to obtain an acrylic acid oligomer for later use;
m4, mixing the acrylic acid oligomer, the ethoxyethoxy ethyl acrylate and the isobornyl acrylate according to a proportion until all components are uniform, so as to obtain the acrylic resin;
in the step M4, the mass ratio of the acrylic oligomer, the ethoxyethoxyethyl acrylate and the isobornyl acrylate in the acrylic resin is 12-19: 8-20: 11.
2. the method for preparing the acrylic optical adhesive film with the three-layer structure for the full-fitting and flexible folding screen, which is characterized by comprising the following steps of: the imidization reaction in the step M1 is carried out at a reaction temperature of 115-130 ℃ for 4-10 hours.
3. The method for preparing the acrylic optical adhesive film with the three-layer structure for the full-fitting and flexible folding screen, which is characterized by comprising the following steps of: and (3) the reaction temperature of the nucleophilic addition reaction in the step M2 is 30-50 ℃, and the reaction time is 0.5-3 h.
4. The method for preparing the acrylic optical adhesive film with the three-layer structure for the full-fitting and flexible folding screen, which is characterized by comprising the following steps of: and (3) the reaction temperature of the polymerization reaction in the step (M3) is 25-35 ℃ and the reaction time is 1.5-4 h.
5. The method for preparing the acrylic optical adhesive film with the three-layer structure for the full-fitting and flexible folding screen, which is characterized by comprising the following steps of: the cross-linking agent in the step S1 is any one of ethylene glycol dimethacrylate, 1, 4-butanediol diacrylate, diethylene glycol diacrylate, allyl methacrylate, 1, 6-hexanediol diacrylate and ethylene glycol diacrylate.
6. The method for preparing the acrylic optical adhesive film with the three-layer structure for the full-fitting and flexible folding screen, which is characterized by comprising the following steps of: and in the step S2, the irradiation amount of ultraviolet rays of the photo-curing is 2100-4000 mJ/cm < 2 >, and the curing time is 5-15 min.
7. An acrylic optical film for a three-layer structure of a fully laminated and flexible folding screen, characterized in that: the method according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211262331.3A CN115404020B (en) | 2022-10-14 | 2022-10-14 | Acrylic optical adhesive film with three-layer structure for full-lamination and flexible folding screen and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211262331.3A CN115404020B (en) | 2022-10-14 | 2022-10-14 | Acrylic optical adhesive film with three-layer structure for full-lamination and flexible folding screen and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115404020A CN115404020A (en) | 2022-11-29 |
| CN115404020B true CN115404020B (en) | 2023-06-30 |
Family
ID=84168628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211262331.3A Active CN115404020B (en) | 2022-10-14 | 2022-10-14 | Acrylic optical adhesive film with three-layer structure for full-lamination and flexible folding screen and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115404020B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117229726B (en) * | 2023-09-25 | 2024-05-14 | 深圳市高仁电子新材料有限公司 | High-performance double-layer-structured acrylic OCA optical adhesive and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1171316A (en) * | 1996-07-31 | 1999-03-16 | Mitsui Chem Inc | Organic optical part having low birefringence and spirobiindane-based polymer |
| CA2634794A1 (en) * | 2005-12-23 | 2007-07-05 | Bristol-Myers Squibb Company | Macrocyclic factor viia inhibitors useful as anticoagulants |
| JP2009230076A (en) * | 2008-03-25 | 2009-10-08 | Kaneka Corp | New photosensitive resin composition, photosensitive resin composition solution obtained therefrom, photosensitive film, insulating film, and printed wiring board with insulating film |
| JP2009233998A (en) * | 2008-03-27 | 2009-10-15 | Ube Ind Ltd | Multilayer structure |
| JP2011126243A (en) * | 2009-12-21 | 2011-06-30 | Ube Industries Ltd | Multilayered structure |
| JP2012102237A (en) * | 2010-11-10 | 2012-05-31 | Dainippon Printing Co Ltd | Polyimide precursor resin composition and article |
| WO2018052104A1 (en) * | 2016-09-15 | 2018-03-22 | ユニチカ株式会社 | Laminated article |
| JP2020097165A (en) * | 2018-12-18 | 2020-06-25 | 三菱ケミカル株式会社 | Laminated film |
| JP2020105247A (en) * | 2018-12-26 | 2020-07-09 | 東洋インキＳｃホールディングス株式会社 | Block polymer and laminate |
| WO2020235164A1 (en) * | 2019-05-22 | 2020-11-26 | 三菱ケミカル株式会社 | Multilayer film |
| WO2022054850A1 (en) * | 2020-09-09 | 2022-03-17 | Ｋｊケミカルズ株式会社 | Solvent for resin synthesis and method for producing synthetic resin using said solvent |
-
2022
- 2022-10-14 CN CN202211262331.3A patent/CN115404020B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1171316A (en) * | 1996-07-31 | 1999-03-16 | Mitsui Chem Inc | Organic optical part having low birefringence and spirobiindane-based polymer |
| CA2634794A1 (en) * | 2005-12-23 | 2007-07-05 | Bristol-Myers Squibb Company | Macrocyclic factor viia inhibitors useful as anticoagulants |
| JP2009230076A (en) * | 2008-03-25 | 2009-10-08 | Kaneka Corp | New photosensitive resin composition, photosensitive resin composition solution obtained therefrom, photosensitive film, insulating film, and printed wiring board with insulating film |
| JP2009233998A (en) * | 2008-03-27 | 2009-10-15 | Ube Ind Ltd | Multilayer structure |
| JP2011126243A (en) * | 2009-12-21 | 2011-06-30 | Ube Industries Ltd | Multilayered structure |
| JP2012102237A (en) * | 2010-11-10 | 2012-05-31 | Dainippon Printing Co Ltd | Polyimide precursor resin composition and article |
| WO2018052104A1 (en) * | 2016-09-15 | 2018-03-22 | ユニチカ株式会社 | Laminated article |
| JP2020097165A (en) * | 2018-12-18 | 2020-06-25 | 三菱ケミカル株式会社 | Laminated film |
| JP2020105247A (en) * | 2018-12-26 | 2020-07-09 | 東洋インキＳｃホールディングス株式会社 | Block polymer and laminate |
| WO2020235164A1 (en) * | 2019-05-22 | 2020-11-26 | 三菱ケミカル株式会社 | Multilayer film |
| WO2022054850A1 (en) * | 2020-09-09 | 2022-03-17 | Ｋｊケミカルズ株式会社 | Solvent for resin synthesis and method for producing synthetic resin using said solvent |
Non-Patent Citations (2)
| Title |
|---|
| Pre-organized molecular tweezer stabilized by intramolecular hydrogen bonds:solvent-responsive host-guest complexation;LV,XQ;TETRAHEDRON LETTERS;第57卷(第18期);1971-1975 * |
| 耐热聚合物研究进展;张国琪;电机电器技术(第02期);67-75 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115404020A (en) | 2022-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104379694B (en) | Polarization plates adhesive composite, with the polarization plates of bonding agent and display device | |
| CN115404020B (en) | Acrylic optical adhesive film with three-layer structure for full-lamination and flexible folding screen and preparation method thereof | |
| CN105462536B (en) | A kind of aqueous silane modified polyurethane adhesive and preparation method thereof | |
| CN101589079A (en) | Curable resin composition and manufacture method thereof | |
| JP2016121215A (en) | Isocyanate group-containing organopolysiloxane compound, method for producing the same, adhesive, tackiness agent, and coating agent | |
| JPWO2018062077A1 (en) | Polymer compound | |
| WO2023098394A1 (en) | Optical-grade oleophilic thermal repair resin, preparation method thereof and self-repairing coating layer | |
| CN110437792A (en) | Optical cement and preparation method thereof suitable for the fitting of curved surface polycarbonate plate | |
| CN112175553A (en) | High-refractive-index OCA (optically clear adhesive) | |
| CN101705067A (en) | Adhesive agent composition for attaching to polarizing plate | |
| CN104726041A (en) | Adhesive composition, polarizer with adhesive, and display device | |
| CN111440573A (en) | Formula of pressure-sensitive adhesive, pressure-sensitive adhesive glue, pressure-sensitive adhesive coating liquid and adhesive tape | |
| CN114133491A (en) | Optical-grade hydrophobic and oleophobic thermal repair resin, preparation method thereof and self-repairing coating | |
| CN113773771A (en) | Pressure-sensitive adhesive with low stripping force and polaroid | |
| CN113388085A (en) | Rosin-based polyurethane glass high polymer material and preparation method thereof | |
| CN103059794B (en) | Bonding glue used for glass mosaics and preparation method thereof | |
| CN116731282A (en) | Washable 3D printing resin and preparation method and application thereof | |
| CN111073579B (en) | High-initial-viscosity polyurethane adhesive for artificial board and preparation method and application thereof | |
| CN115368867B (en) | Environment-friendly UV adhesive, preparation method thereof and application thereof in label paper | |
| CN107868582B (en) | Ultraviolet-curing normal-temperature curtain coating glossy white finish | |
| TWI688581B (en) | (Meth)acrylate resin manufacturing method, optical member manufacturing method, curable composition manufacturing method, cured product manufacturing method | |
| CN115287023A (en) | OCA optical cement with high refractive index and preparation method thereof | |
| CN104650314A (en) | Dual-curing organic fluorine modified polyurethane pre-polymer and preparation method thereof as well as ultraviolet photo-cured membrane manufactured by polyurethane pre-polymer | |
| CN110903459B (en) | Hydroxyl-terminated polyurethane methacrylic resin, preparation method and application thereof | |
| CN115029055A (en) | Weather-resistant modified polyurethane waterproof coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |