CN112251172A - Optical adhesive layer, method of preparing the same, optical adhesive and flexible display device - Google Patents
Optical adhesive layer, method of preparing the same, optical adhesive and flexible display device Download PDFInfo
- Publication number
- CN112251172A CN112251172A CN202011060926.1A CN202011060926A CN112251172A CN 112251172 A CN112251172 A CN 112251172A CN 202011060926 A CN202011060926 A CN 202011060926A CN 112251172 A CN112251172 A CN 112251172A
- Authority
- CN
- China
- Prior art keywords
- optical adhesive
- adhesive layer
- acrylate
- weight
- meth
- 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.)
- Pending
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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1805—C5-(meth)acrylate, e.g. pentyl (meth)acrylate
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an optical adhesive layer and a preparation method thereof, belonging to the technical field of polymer synthesis. Specifically, the optical adhesive layer contains an ultra-high molecular weight (meth) acrylate polymer and an additive; the additive is 0.01-20 parts by weight based on 100 parts by weight of the (meth) acrylate polymer; the (methyl) acrylate polymer is prepared by adopting an emulsion polymerization method, and the weight average molecular weight is more than 300 ten thousand. The optical adhesive layer prepared by the invention has the advantages of environment-friendly synthesis process, small environmental pollution, good film forming property and strong durability, and can fully fit with the physical properties required by the current flexible display device when being applied to the market as an optical adhesive.
Description
Technical Field
The invention belongs to the technical field of high-molecular adhesives, and particularly relates to an optical adhesive layer and a preparation method thereof, an optical adhesive with the adhesive layer, and a flexible display device using the optical adhesive.
Background
Common applications for pressure sensitive adhesives in industry today are the manufacture of various displays such as computer monitors, televisions, mobile phones, and small displays (in automobiles, appliances, wearable objects, electronic devices, etc.). Flexible electronic displays, in which the display can be bent freely without cracking or breaking, are a rapidly emerging field of technology for fabricating electronic devices using, for example, flexible plastic substrates. This technology allows integration of electronic functionality into non-planar objects, compliance with desired designs, and flexibility during use, which can lead to a large array of new applications.
With the advent of flexible electronic displays, there has been an increasing demand for adhesives, particularly Optically Clear Adhesives (OCAs), in flexible display devices, due to the fact that the devices themselves are bent, rolled or folded, to serve as an assembly layer or gap-filling layer between the outer cover lens or sheet (based on glass, PET, PC, PMMA, polyimide, PEN, cyclic olefin copolymer, etc.) and the underlying display module of the electronic display assembly. The presence of the OCA improves the performance of the display by increasing brightness and contrast while also providing structural support for the assembly. In flexible assemblies, the OCA will also be used for assembly layers, which, in addition to the typical OCA function, can absorb most of the folding induced stress to prevent damage to fragile parts of the display panel and to protect electronic components from breaking under folding stress.
Most of the existing OCA optical adhesives are solvent-based optical adhesives, and because organic solvents such as toluene, ethyl acetate and the like are adopted for synthesis, the environmental protection property is poor.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an optical adhesive layer using an ultrahigh molecular weight (methyl) acrylate polymer as a substrate, which has the advantages of environment-friendly synthesis process, small environmental pollution, good film forming property and strong durability, and can fully meet the physical properties required by the current flexible display device.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present disclosure is an optical adhesive layer comprising an ultra-high molecular weight (meth) acrylate polymer and an additive;
the additive is 0.01-20 parts by weight based on 100 parts by weight of the (meth) acrylate polymer; the (methyl) acrylate polymer is prepared by adopting an emulsion polymerization method, and the weight average molecular weight is more than 300 ten thousand.
Further, the (meth) acrylate polymer of the present invention contains the following raw material components in parts by weight: 100 parts by weight of (methyl) acrylate monomer, 1-4 parts by weight of emulsifier, 0.2-0.4 part by weight of pH regulator, 0.1-1 part by weight of initiator and 100-300 parts by weight of water.
Further, in the optical adhesive layer of the present invention, the method for synthesizing the (meth) acrylate polymer comprises:
1) preparing a seed emulsion: firstly, 30-40 wt% of water and 20-40 wt% of various (methyl) acrylate monomers are added, and the weight ratio of the water to the monomers is controlled to be 1: 0.7-0.9; adding an emulsifier and a pH regulator; then adding 60-100% of initiator by weight; stirring and heating to 20-40 ℃ under the protection of nitrogen;
2) and (3) segmented polymerization reaction: after the reaction is heated up, the (methyl) acrylate monomer with the rest weight is added in multiple sections, and the temperature is kept between 50 and 60 ℃; adding the rest amount of water for many times, heating to 80-85 deg.C, and adding the rest amount of initiator; then cooling to 20-35 ℃ to obtain the (methyl) acrylate polymer.
Further, in the optical adhesive layer of the present invention, the (meth) acrylate monomer is selected from methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid, hydroxyethyl acrylate, and methacrylic acid.
Further, in the optical adhesive layer of the present invention, butyl acrylate is used in an amount of 60% to 100% based on the total amount of all acrylates.
Further, in the optical adhesive layer of the present invention, the emulsifier is selected from sodium dodecylbenzenesulfonate, sodium hexadecylbenzenesulfonate, and sodium hexadecylsulfate.
Further, in the optical adhesive layer of the present invention, the pH adjuster is selected from sodium hydroxide, sodium bicarbonate, and potassium hydroxide.
Further, in the optical adhesive layer according to the present invention, the initiator is selected from the group consisting of ammonium persulfate, potassium persulfate, and sodium dithionite.
Further, in the optical adhesive layer of the present invention, the number of stages in the stage polymerization reaction is 5 to 30 stages, and the interval between each stage is 3 to 10 minutes.
Further, in the optical adhesive layer of the present invention, a metal particle complexing agent is added during the seed emulsion polymerization in an amount of 2 to 4 parts per million of the (meth) acrylate monomer.
Further, in the optical adhesive layer according to the present invention, the metal particle complexing agent is selected from copper sulfate and ferrous sulfate.
In a second aspect, the present invention further provides a method for preparing an optical adhesive layer, for preparing the optical adhesive layer according to the first aspect, specifically including the following steps:
1) dewatering and demulsifying the (methyl) acrylate polymer, and then drying and granulating;
2) carrying out hot-melt mixing on the (methyl) acrylate polymer obtained after granulation and an additive through a double-screw hot-melt extruder, and controlling the temperature and the addition rate to ensure full mixing;
3) the optical adhesive layer was obtained by hot melt coating through a "T" type extrusion head.
Further, the preparation method can also comprise the following steps:
1) dehydrating and demulsifying the (methyl) acrylate polymer;
2) then dissolving in alcohol, and further displacing to remove water;
3) then mixing the mixture into an organic solvent for full dissolution, adding an additive, and fully stirring and mixing to obtain a solvent type acrylate adhesive;
4) and coating the solvent-based acrylate adhesive to obtain the optical adhesive layer.
In a third aspect, the present invention also provides an optical adhesive comprising the optical adhesive layer according to the first aspect.
In a fourth aspect, the present invention also provides a flexible display device, which contains the optical adhesive according to the third aspect.
Compared with the prior art, the invention has the advantages that:
1. the invention prepares the optical adhesive layer with ultra-high molecular weight (more than 300 ten thousand) by emulsion polymerization and demulsification dehydration; the synthetic process has strong stability and little environmental pollution, and the synthesized glue has good film forming property and strong durability, and the conversion rate reaches more than 98 percent.
2. When the optical adhesive composition provided by the invention is applied to a flexible display device as an optical adhesive, the optical adhesive composition can show good curling resistance and bending resistance, and can fully meet the requirements of the current flexible display device.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The "(meth) acrylate polymer" as referred to in the present invention is to be understood as "acrylate polymer" and/or "(meth) acrylate polymer"; the "(meth) acrylate monomer" is understood to mean "acrylate monomer" and/or "(meth) acrylate monomer".
As the optical adhesive layer described in the present invention, at least a (meth) acrylate polymer and an additive; the additives may be crosslinking agents, tackifiers, coupling agents, and ionic compounds. The additive should be contained in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the (meth) acrylate polymer.
Examples of the alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylate polymer include alkyl (meth) acrylates having 1 to 18 carbon atoms in a linear or branched alkyl group. For example, the above alkyl group may be exemplified by: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, isooctyl, nonyl, decyl, isodecyl, dodecyl, isomyristyl, lauryl, tridecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and the like. These may be used alone or in combination.
The (meth) acrylate polymer uses a (meth) acrylate containing an aromatic ring. The aromatic ring-containing (meth) acrylate is a compound having an aromatic ring structure in its structure and containing a (meth) acryloyl group. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and a biphenyl ring. The aromatic ring-containing (meth) acrylate satisfies durability and improves display unevenness caused by white discharge at the peripheral portion.
Specific examples of the aromatic ring-containing (meth) acrylate include: (meth) acrylates having a benzene ring such as benzyl (meth) acrylate, phenyl (meth) acrylate, o-phenylphenol (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, ethylene oxide-modified cresol (meth) acrylate, phenol ethylene oxide-modified (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, tolyl (meth) acrylate, polystyrene-based (meth) acrylate, and the like; (meth) acrylates having a naphthalene ring such as hydroxyethylated β -naphthol acrylate, 2-naphthoethyl (meth) acrylate, 2-naphthyloxyethyl acrylate, and 2- (4-methoxy-1-naphthyloxy) ethyl (meth) acrylate; and (meth) acrylates having a biphenyl ring such as biphenyl (meth) acrylate.
The aromatic ring-containing (meth) acrylate is preferably benzyl (meth) acrylate or phenoxyethyl (meth) acrylate, and particularly preferably phenoxyethyl (meth) acrylate, from the viewpoint of adhesion characteristics and durability.
When the acrylate polymer is applied to the invention, the acrylate polymer should contain the following raw material components in parts by weight: 100 parts by weight of (methyl) acrylate monomer, 1-4 parts by weight of emulsifier, 0.2-0.4 part by weight of pH regulator, 0.1-1 part by weight of initiator and 100-300 parts by weight of water.
The (meth) acrylic ester monomer is selected from methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid, hydroxyethyl acrylate and methacrylic acid.
The emulsifier is selected from sodium dodecyl benzene sulfonate, sodium hexadecylbenzene sulfonate and sodium hexadecyl sulfate; preferably sodium dodecylbenzene sulfonate (ABS); in emulsion polymerization, the emulsifier forms countless micelles in a water phase to become a polymerization place, and after the reaction is finished, the emulsifier is adsorbed around the micelles with infinite sizes so as to prevent collision and coagulation among the micelles and play a role in dispersion and stabilization; however, the emulsion needs to be effectively broken in the synthesis process; therefore, the emulsion is stable enough in the combination process, does not generate coagulum and delamination, and is easy to break after discharging; therefore, the anionic emulsifier is selected, has strong emulsifying capacity and good centrifugal stability, is not easy to generate coagulum during polymerization, but has poor chemical stability and is easy to demulsify; anionic emulsifiers are desirable in terms of their chemical stability relative to nonionic emulsifiers; and the emulsifier preferably has a solids content of 25-35%, more preferably 30%.
The pH regulator is selected from sodium hydroxide, sodium bicarbonate and potassium hydroxide; sodium hydroxide is preferred.
The initiator is selected from ammonium persulfate, potassium persulfate and sodium hydrosulfite; preferably potassium persulfate, sodium dithionite.
The acrylate polymer is an ultrahigh molecular weight acrylate polymer, and the weight average molecular weight of the acrylate polymer is more than 300 ten thousand; the specific synthesis method comprises the following steps:
1) preparing a seed emulsion: firstly, 30-40 wt% of water and 20-40 wt% of various (methyl) acrylate monomers are added, and the weight ratio of the water to the monomers is controlled to be 1: 0.7-0.9; adding an emulsifier and a pH regulator; then adding 60-100% of initiator by weight; stirring and heating to 20-40 ℃ under the protection of nitrogen;
2) and (3) segmented polymerization reaction: after the reaction is heated up, the (methyl) acrylate monomer with the rest weight is added in multiple sections, and the temperature is kept between 50 and 60 ℃; adding the rest amount of water for many times, heating to 80-85 deg.C, and adding the rest amount of initiator; then cooling to 20-35 ℃; obtaining the acrylate polymer.
Wherein, a metal particle complexing agent which is 2-4 parts by million of the addition of the acrylate monomer is added during the seed emulsion polymerization for improving the reaction rate and reducing the induction period; preferably, the metal particle complexing agent is selected from copper sulfate and ferrous sulfate. If no metal particle complexing agent is added, the reaction temperature can be increased by 50-55 ℃, and the reaction rate is ensured.
In addition, the optical adhesive layer is prepared into the acrylate polymer by adopting an emulsion polymerization method, but for the optical adhesive, small molecules such as water and an emulsifier can influence the performances such as light transmittance and the like of the adhesive; the present invention thus provides a process for the preparation of two optical adhesives:
the first method specifically comprises the following steps:
1) dehydrating and demulsifying the acrylate polymer, and then drying and granulating;
2) carrying out hot-melt mixing on the acrylate polymer obtained after granulation and an additive through a double-screw hot-melt extruder, controlling the temperature and the addition rate, and ensuring full mixing;
3) the optical adhesive layer was obtained by hot melt coating through a "T" type extrusion head.
The second method specifically comprises the following steps:
1) dehydrating and demulsifying an acrylate polymer;
2) then dissolving in alcohol, and further displacing to remove water;
3) then mixing the mixture into an organic solvent for full dissolution, adding an additive, and fully stirring and mixing to obtain a solvent type acrylate adhesive;
4) and coating the solvent-based acrylate adhesive to obtain the optical adhesive layer.
What is most important in the above steps is how to break and remove water, and for this reason, the following method can be adopted: the following method is a laboratory theoretical method and an industrial application method, and can be adjusted according to actual conditions so as to meet the requirements as a reference:
experiments show that the demulsification method can be divided into the following steps: heat treatment demulsification, chemical demulsification, electric treatment demulsification, physical demulsification and the like. The specific demulsification method is studied as follows.
Firstly, adding metal ion electrolyte (AL)3+) Emulsion polymerization using anionic surfactant as emulsifier, wherein the emulsifier molecules are adsorbed and surrounded around the colloidal particles (O/W type) when the reaction is stopped. Because of the hydrophilicity, the colloidal particles are actually surrounded by a layer of negative charges, so that a diffusion double electric layer with a certain potential is formed, and the O/W colloidal particles are stabilized by the electrostatic repulsion potential between the colloidal particles, wherein the higher the potential is, the more stable the emulsion is. Adding metal ion electrolyte (AL)3+) The counter ions will press the effective thickness of the double electric layer, lowering the potential, causing the emulsion to lose balance and even breaking. At the same time, the counter ions are squeezed into the surfactant ion array, so that a thin equipotential layer is generated, and the original stable colloidal particles can be coagulated mutually to break emulsion.
And secondly, adding a cationic surfactant and polyacrylamide (CPAM), selecting the Cationic Polyacrylamide (CPAM) as a demulsifier according to the characteristic that the main added component in the emulsion is the anionic surfactant, adjusting the CPAM adding amount, the stirring speed and the reaction time of the selected emulsion, and taking COD (chemical oxygen demand), oil content and suspended matter (SS) removal rate as emulsion breaking effect evaluation indexes of the emulsion to finally determine that the CPAM adding amount is 0.25g/L, reacting for 10min under the stirring of 150r/min, wherein the COD, the oil content and the SS removal rate are 75.37%, 97.04% and 100%, and the oil, the SS and the added demulsifier are removed in the form of black-cluster-shaped viscous oil sludge, so that the oil-water separation is convenient, rapid and efficient. The calorific value of the oil sludge is as high as 35992kj/kg, which is higher than that of raw coal (20934kj/kg), and the oil sludge can be used as an alternative fuel. The CPAM has certain universality as an emulsion wastewater demulsifier.
Thirdly, demulsification by heat treatment: emulsions are thermodynamically unstable systems. Although increasing the temperature has little effect on the electric double layer of the emulsion and the interfacial adsorption. However, in thermodynamic considerations, if the temperature is increased, the thermal motion of the interface molecules is increased, the interface viscosity is reduced, and the molecular arrangement of the interface film is loosened, which is favorable for the aggregation of liquid beads. In addition, the increase in temperature reduces the viscosity of the external phase, thereby reducing the stability of the emulsion and facilitating the breaking of the emulsion. Heating can be used as a means of breaking the emulsion, particularly for non-ionically stabilized O/W crude oil emulsions, where the hydrophilicity of the emulsion decreases at elevated temperatures and the emulsion is quickly broken when the temperature is raised to the phase transition temperature. On the contrary, for W/O type emulsion stabilized by nonionic surfactant, when the temperature is reduced to the phase transition temperature, the emulsion is also destroyed quickly. The heat treatment method has simple principle and stronger adaptability.
Fourthly, micro-channel demulsification: the device mainly utilizes the property of the demulsifying substance, adopts gravity or centrifugation and other modes to carry out multidirectional separation, is cleaner than the environment, is simple, and has low production cost after being standardized. For example, in journal "Mazheng Dong, Wemeixiu, etc., demulsification research of a spiral plate type micro-channel with super-large aspect ratio on O/W type emulsion" proposed in the chemical engineering Proc. 2020.09.09 ", the demulsification process of oil-in-water (O/W) type emulsion is strengthened by utilizing the coupling effect between the oleophylic and hydrophobic surface in the micro-channel and the three-dimensional spiral microstructure. The influence of the number of micro-channel pieces, the volume flow rate of the emulsion and the residence time on the emulsion breaking rate is researched by combining a computer simulation method. The experimental results show that: with the increase of the number of the micro-channels, the demulsification rate is increased, and the particle size of the demulsified liquid drops is gradually reduced; along with the increase of the volume flow rate of the emulsion liquid, the emulsion breaking rate shows the trend of rising firstly and then falling, the coupling effect of the surface effect of the channel and the Dean vortex effect is reflected, and the maximum single emulsion breaking rate is 25 percent; the demulsification rate increases along with the increase of the retention time, and after 7 times of circulating demulsification, the maximum demulsification rate is 85.9 percent. It was found by computer simulation that: along with the increase of the flow velocity, the number and the strength of Dean vortexes in the rectangular cross section of the microchannel are increased, the vortex area is continuously expanded towards the upper wall surface and the lower wall surface, when the volume flow velocity is 8mL/min, the number of Dean vortexes reaches 2 pairs at most, the wall surface shearing rate is 5527s < -1 > at the moment, the maximum emulsion breaking rate is reached, the flow velocity is further improved, and the emulsion breaking rate is reduced due to the fact that the shearing rate at the wall surface and the Dean vortexes are disturbed excessively.
The four demulsification methods shown above are only used for characterizing the demulsification method of the invention and are not limited in the protection scope of the invention. The method should be selected reasonably according to actual production conditions and performance requirements.
As the optical glue shown herein, it should have at least the optical adhesive layer disclosed herein; and the optical adhesive layer is prepared by the preparation method disclosed by the invention.
The test method of the evaluation parameters related to the present invention is shown below:
1) molecular weight test method:
as measured by Gel Permeation Chromatography (GPC), and also by intrinsic viscosity.
2) The light transmittance test method comprises the following steps:
the test method is standard according to ASTM-D1003.
3) Peel force test method:
the test method is standard according to ASTM-D3330.
4) Room temperature modulus test method:
the test was carried out using the DMA test method, at a test temperature of 25 ℃.
5) Dynamic bending test method:
the liner was removed from the 2 mil thick assembly layer and the material was laminated between two 1.7 mil polyimide sheets to form a 3-layer construction. The laminate was then cut to 5 "length x 1" width. A5-layer construction consisting of PI/AS/PI/AS/PI was also prepared in a similar manner with a 2 mil assembly layer and 1.7 mil PI. The sample was mounted in a dynamic folding apparatus with two folding stages that rotated from 180 degrees (i.e., the sample was not bent) to 0 degrees (i.e., the sample is now folded) and was tested at a rate of about 6 cycles/minute. The 5mm bend radius is determined by the gap between the two rigid plates in the closed state (0 degrees). No mandrel is used to guide the curvature (i.e., a free-form bend is used). Folding was performed at room temperature.
6) Static curl test method:
the sample is cut into 3mm-5mm small samples, placed in a 55 ℃/95RH environment for five days in a curling mode, and whether bubbles exist or not is observed.
The beneficial effects of the present invention are characterized below in specific examples (as shown in table 1):
table 1:
description of the data: as can be seen from examples 1 to 5 above, the weight average molecular weight of the acrylate polymer obtained by the method for synthesizing an acrylate polymer according to the present invention can be 300 ten thousand or more.
The acrylate polymers prepared in the above examples 1 to 5 were used to prepare an optical adhesive layer by the method for preparing an optical adhesive layer according to the present invention, and light transmittance, peeling force, modulus, dynamic bending, and static curling experiments were performed, respectively; the test data are shown in the following table: (as shown in Table 2)
Table 2:
description of the data: as can be seen from table 2, the optical cement produced according to the present invention has a light transmittance of 90% or more and is excellent in adhesion and bending resistance.
The description and illustrations of the embodiments described herein are intended to provide a general understanding of the structure of various embodiments. The specification and illustrations are not intended to serve as an exhaustive and comprehensive description of all the elements and features of apparatus and systems that utilize the structures or methods described herein. Separate embodiments may also be provided in combination in a single embodiment, and conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination.
Further, reference to values stated in ranges includes each and every value within that range. Many other embodiments will be apparent to those of skill in the art upon reading this specification only. Other embodiments may be used and derived from the disclosure, such that a structural substitution, logical substitution, or another change may be made without departing from the scope of the disclosure. The present invention is, therefore, to be considered as illustrative and not restrictive.
Claims (15)
1. An optical adhesive layer, characterized in that the optical adhesive layer contains an ultra-high molecular weight (meth) acrylate polymer and an additive;
the additive is 0.01-20 parts by weight based on 100 parts by weight of the (meth) acrylate polymer;
the (methyl) acrylate polymer is prepared by adopting an emulsion polymerization method, and the weight average molecular weight is more than 300 ten thousand.
2. An optical adhesive layer according to claim 1, wherein the (meth) acrylate polymer comprises the following raw material components in parts by weight:
100 parts by weight of (methyl) acrylate monomer, 1-4 parts by weight of emulsifier, 0.2-0.4 part by weight of pH regulator, 0.1-1 part by weight of initiator and 100-300 parts by weight of water.
3. An optical adhesive layer according to claim 2, wherein the (meth) acrylate polymer is synthesized by:
1) preparing a seed emulsion: firstly, 30-40 wt% of water and 20-40 wt% of various (methyl) acrylate monomers are added, and the weight ratio of the water to the monomers is controlled to be 1: 0.7-0.9; adding an emulsifier and a pH regulator; then adding 60-100% of initiator by weight; stirring and heating to 20-40 ℃ under the protection of nitrogen;
2) and (3) segmented polymerization reaction: after the reaction is heated up, the (methyl) acrylate monomer with the rest weight is added in multiple sections, and the temperature is kept between 50 and 60 ℃; adding the rest amount of water for many times, heating to 80-85 deg.C, and adding the rest amount of initiator; then cooling to 20-35 ℃ to obtain the (methyl) acrylate polymer.
4. An optical adhesive layer according to claim 2 or 3, wherein said (meth) acrylate monomer is selected from methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid, hydroxyethyl acrylate, methacrylic acid.
5. An optical adhesive layer according to claim 4, wherein butyl acrylate is used in an amount of 52% to 100% based on the total amount of all (meth) acrylate monomers.
6. An optical adhesive layer according to claim 2 or 3, wherein said emulsifier is selected from sodium dodecylbenzenesulfonate, sodium hexadecylbenzenesulfonate and sodium hexadecylsulfate.
7. An optical adhesive layer according to claim 2 or 3, wherein said pH adjusting agent is selected from the group consisting of sodium hydroxide, sodium bicarbonate, and potassium hydroxide.
8. An optical adhesive layer according to claim 2 or 3, wherein said initiator is selected from the group consisting of ammonium persulfate, potassium persulfate, and sodium dithionite.
9. An optical adhesive according to claim 3, wherein the number of stages in the staged polymerisation is from 5 to 30 stages, each stage being spaced apart by from 3 to 10 minutes.
10. An optical adhesive layer according to claim 3, wherein a metal particle complexing agent is added during the seeded emulsion polymerization in an amount corresponding to 2-4 parts per million of the (meth) acrylate monomer addition.
11. An optical adhesive layer according to claim 10, wherein said metal particle complexing agent is selected from copper sulfate and ferrous sulfate.
12. A method for producing an optical adhesive layer, for producing an optical adhesive layer according to claims 1 to 11, comprising the steps of:
1) dewatering and demulsifying the (methyl) acrylate polymer, and then drying and granulating;
2) carrying out hot-melt mixing on the (methyl) acrylate polymer obtained after granulation and an additive through a double-screw hot-melt extruder, and controlling the temperature and the addition rate to ensure full mixing;
3) the optical adhesive layer was obtained by hot melt coating through a "T" type extrusion head.
13. A method for producing an optical adhesive layer, for producing an optical adhesive layer according to claims 1 to 11, comprising the steps of:
1) dehydrating and demulsifying the (methyl) acrylate polymer;
2) then dissolving in alcohol, and further displacing to remove water;
3) then mixing the mixture into an organic solvent for full dissolution, adding an additive, and fully stirring and mixing to obtain a solvent type acrylate adhesive;
4) and coating the solvent-based acrylate adhesive to obtain the optical adhesive layer.
14. An optical adhesive comprising the optical adhesive layer according to claims 1 to 11.
15. A flexible display device comprising the optical adhesive according to claim 14.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011060926.1A CN112251172A (en) | 2020-09-30 | 2020-09-30 | Optical adhesive layer, method of preparing the same, optical adhesive and flexible display device |
| PCT/CN2021/109138 WO2022068353A1 (en) | 2020-09-30 | 2021-07-29 | Optical adhesive layer and production method therefor, optical clear adhesive, and flexible display device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011060926.1A CN112251172A (en) | 2020-09-30 | 2020-09-30 | Optical adhesive layer, method of preparing the same, optical adhesive and flexible display device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112251172A true CN112251172A (en) | 2021-01-22 |
Family
ID=74233645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011060926.1A Pending CN112251172A (en) | 2020-09-30 | 2020-09-30 | Optical adhesive layer, method of preparing the same, optical adhesive and flexible display device |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN112251172A (en) |
| WO (1) | WO2022068353A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113429915A (en) * | 2021-07-16 | 2021-09-24 | 江苏艾科赛特新材料有限公司 | Aqueous formaldehyde-free adhesive special for artificial board and preparation method thereof |
| WO2022068353A1 (en) * | 2020-09-30 | 2022-04-07 | 江苏斯迪克新材料科技股份有限公司 | Optical adhesive layer and production method therefor, optical clear adhesive, and flexible display device |
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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051131A (en) * | 2009-10-27 | 2011-05-11 | 琳得科株式会社 | Optical adhesive composition, optical adhesive and optical film |
| US20200032114A1 (en) * | 2016-09-30 | 2020-01-30 | Nitto Denko Corporation | Optical adhesive layer, manufacturing method of optical adhesive layer, optical film with adhesive layer, and image display device |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4481020B2 (en) * | 2004-01-22 | 2010-06-16 | 日東電工株式会社 | Optical member adhesive composition, optical member adhesive layer, optical member adhesive sheet, and optical member |
| CN101338005B (en) * | 2008-03-11 | 2011-03-30 | 郑勇 | Process for synthesizing acrylic ester copolymer of ultra-high molecular mass |
| JP5336323B2 (en) * | 2009-10-23 | 2013-11-06 | 日東電工株式会社 | Adhesive layer for optical film, adhesive optical film, and image display device |
| WO2011070870A1 (en) * | 2009-12-09 | 2011-06-16 | 日東電工株式会社 | Adhesive layer for optical film, adhesive optical film, process for production of the adhesive optical film, and image display device |
| KR102205896B1 (en) * | 2018-02-06 | 2021-01-21 | 주식회사 엘지화학 | Optical member and flexible display apparatus comprising the same |
| CN112251172A (en) * | 2020-09-30 | 2021-01-22 | 江苏斯迪克新材料科技股份有限公司 | Optical adhesive layer, method of preparing the same, optical adhesive and flexible display device |
-
2020
- 2020-09-30 CN CN202011060926.1A patent/CN112251172A/en active Pending
-
2021
- 2021-07-29 WO PCT/CN2021/109138 patent/WO2022068353A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051131A (en) * | 2009-10-27 | 2011-05-11 | 琳得科株式会社 | Optical adhesive composition, optical adhesive and optical film |
| US20200032114A1 (en) * | 2016-09-30 | 2020-01-30 | Nitto Denko Corporation | Optical adhesive layer, manufacturing method of optical adhesive layer, optical film with adhesive layer, and image display device |
| US20200239743A1 (en) * | 2016-09-30 | 2020-07-30 | Nitto Denko Corporation | Optical adhesive layer, manufacturing method of optical adhesive layer, optical film with adhesive layer, and image display device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022068353A1 (en) * | 2020-09-30 | 2022-04-07 | 江苏斯迪克新材料科技股份有限公司 | Optical adhesive layer and production method therefor, optical clear adhesive, and flexible display device |
| CN113429915A (en) * | 2021-07-16 | 2021-09-24 | 江苏艾科赛特新材料有限公司 | Aqueous formaldehyde-free adhesive special for artificial board and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2022068353A1 (en) | 2022-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112251172A (en) | Optical adhesive layer, method of preparing the same, optical adhesive and flexible display device | |
| CN101622322B (en) | Adhesive, double-sided adhesive sheet and display | |
| CN105518094B (en) | Electronic equipment bonding sheet | |
| EP1882707B1 (en) | bimodal acrylate adhesive mass for gluing low energy and rough surfaces | |
| EP2445981B1 (en) | Sebum resistant polyacrylate adhesive tapes for adhesing windows in mobile phones | |
| KR20160010545A (en) | Multilayer pressure sensitive adhesive assembly | |
| CN106519106A (en) | Super-transparent acrylate pressure-sensitive adhesive emulsion capable of being coated at high speed as well as preparation method and application thereof | |
| CN103764781A (en) | Adhesive, adhesive layer and adhesive sheet | |
| CN102504733A (en) | Water-blush-resistant fluoride and siloxane modified waterborne pressure-sensitive adhesive and polyethylene protective film | |
| CN111087950A (en) | Adhesive, double-sided tape applying adhesive and preparation method of double-sided tape | |
| JP2016000774A (en) | Pressure sensitive adhesive sheet and bonded body using the same | |
| CN211896779U (en) | Self-exhaust double-sided tape | |
| KR20210079375A (en) | adhesive tape | |
| JP2005314534A (en) | Acrylic resin film, laminated film and optical filter | |
| CN103013403A (en) | Nano-emulsion pressure-sensitive adhesive and preparation method thereof | |
| CN111154429A (en) | Polyacrylate pressure-sensitive adhesive | |
| WO2021085136A1 (en) | Adhesive agent composition, adhesive sheet, and optical member | |
| KR20140080484A (en) | Vinyl polymer microparticles, method for producing same, resin composition, and optical material | |
| CN103382236A (en) | Silicone-acrylate emulsion with high organosilicon content and preparation method thereof | |
| TW201516112A (en) | Reversible pressure-sensitive adhesive mass | |
| WO2017138609A1 (en) | Uv curable acrylic polymer and method for producing same, and uv curable hot melt adhesive | |
| KR100552888B1 (en) | Thermosetting Powder Coating Composition, Method for Forming Coating Film of the Composition, and Coating Film | |
| EP2521739B1 (en) | Multimodal copolymers, process of production and use in pressure sensitive adhesives | |
| KR101831076B1 (en) | Liquid crystal sealing agent, and method for manufacturing liquid crystal display panel | |
| CN113122076A (en) | Graphite oxide allyl acid emulsion, preparation method thereof and water-based paint |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210122 |
|
| RJ01 | Rejection of invention patent application after publication |