CN114214006B - OCA optical glue with high filling property and OCA optical adhesive film - Google Patents
OCA optical glue with high filling property and OCA optical adhesive film Download PDFInfo
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- CN114214006B CN114214006B CN202111634060.5A CN202111634060A CN114214006B CN 114214006 B CN114214006 B CN 114214006B CN 202111634060 A CN202111634060 A CN 202111634060A CN 114214006 B CN114214006 B CN 114214006B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J133/24—Homopolymers or copolymers of amides or imides
- C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J133/24—Homopolymers or copolymers of amides or imides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- 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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/403—Adhesives in the form of films or foils characterised by release liners characterised by the structure of the release feature
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- 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
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- Adhesives Or Adhesive Processes (AREA)
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Abstract
The invention discloses high-filling OCA optical glue and an OCA optical glue film, wherein the raw materials of the OCA optical glue comprise a polymer, and at least two components of a solvent, a cross-linking agent, a photoinitiator and an antioxidant, wherein the polymer has a weight average molecular weight of 100000-2000000 daltons and a glass transition temperature of-60-0 ℃, the intrinsic viscosity of the polymer is 0.30-0.70, and the polymer is obtained by polymerizing the raw materials comprising the following components in parts by weight: 40-80 parts of low Tg long-chain branched (methyl) acrylate monomer, 10-40 parts of high Tg (methyl) acrylate monomer, 1-15 parts of hydroxyl (methyl) acrylate monomer, 1-20 parts of functional acrylate monomer and 0.1-5 parts of branched monomer. The prepared adhesive film achieves the industry high standard in the performances of attaching, filling, transporting and storing, inhibiting reverse foaming and the like, and is also suitable for filling large-depth and more complex designs, such as filling holes, curved surfaces, flexible electronic equipment and other scenes.
Description
Technical Field
The invention relates to the technical field of glue, in particular to high-filling OCA optical glue and an OCA optical glue film.
Background
The optical transparent adhesive OCA (optical clear adhesive) is a novel material which is applied to display equipment mainly comprising liquid crystal and has the composite functions of light transmission, light homogenization, display enhancement, protection and the like. Depending on the product morphology, the broad OCAs can be further classified into OCR (optically clear resins), OCA (optically clear adhesive films) and LOCA (i.e., liquid optical adhesives-OCAs currently tend to be ink-jet printed). The earliest OCA was proposed by hitachi formation and the like in the form of OCR, and was developed into a mainstream OCA film product in the current market by the company of minnesota mining and manufacturing (3M) in the united states, mitsubishi chemical company in japan and the like (patent nos. WO2011129200A1, US20030064188A1, WO2009131792A1, US5520978a, CN 101998982A). As a basic requirement, the OCA adhesive film must be ensured to be absolutely clean and stable in the manufacturing process, the surface of the substrate must be fully soaked in a short time in the bonding process, all air is removed, the OCA has good adhesion capability to substrates with different surface energy on two sides, and the aging process must resist long-time UV, water vapor, heat, temperature change and other environmental comprehensive factors.
China is the largest electronic product production area in the world at present, but the supply chain of OCAs is in a monopolized state by foreign resources. According to market conservation estimation, the market share of only 3M and Mitsubishi two companies in China is more than 90%. The reason for monopoly of the material is complex. Firstly, OCA is different from common adhesives, except the uniqueness of a formula, the OCA has extremely high requirements on the whole set of preparation process, and the production cost, performance and market competitiveness of related electronic products are directly determined by the product yield and the effect stability before and after use; furthermore, a few companies invest a lot of time and cost in the development of OCA, the related technology is monopolized, and on the premise of no independent IP support, new domestic competitors lack independent intellectual property protection, so that the subsequent long-term innovation and development are affected.
On the other hand, the demand for OCAs in the related industry is huge. With the rapid iteration and derivatization of electronic products, the demand trend for OCA performance is becoming integrated and optimized. This results in the conventional OCA failing to meet new requirements; meanwhile, along with the development and production of electronic products, which are the first world in China, the demand of OCA (optical clear-cut) is increased. The autonomous development, iteration and production capacity of OCA products is one of the material bottlenecks that limit the development of the electronics technology industry.
Under the background, in combination with specific requirements of industries, development of a high-performance OCA with independent intellectual property rights is urgently needed to enable the product to meet basic performance requirements of the OCA, and meanwhile transportation stability, flexible matching of a bonding process, excellent filling performance, stability of a production process and certain universality are considered.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides OCA optical glue with high filling property.
In order to achieve the above purpose, the invention adopts the following technical scheme: the OCA optical glue with high filling property comprises a polymer, and at least two components of a solvent, a cross-linking agent, a photoinitiator and an antioxidant, wherein the polymer has a weight average molecular weight of 100000-2000000 daltons (hereinafter abbreviated as D) and a glass transition temperature in a range of-60-0 ℃, the intrinsic viscosity of the polymer is in a range of 0.30-0.70, and the polymer is obtained by polymerizing the following raw materials in parts by weight: 40-80 parts of low Tg long-chain branched (methyl) acrylate monomer, 10-40 parts of high Tg (methyl) acrylate monomer, 1-15 parts of hydroxyl (methyl) acrylate monomer, 1-20 parts of functional acrylate monomer and 0.1-5 parts of branched monomer.
Preferably, the polymer has a weight average molecular weight of 300000-1500000 daltons, a glass transition temperature in the range of-50-0 ℃ and an intrinsic viscosity in the range of 0.40-0.50. In the prepared glue, the characteristic viscosity number (IV) of the product is required to be between 0.3 and 0.7, if the viscosity number (IV) is lower than 0.3, the cohesive force of the glue can be seriously problematic, and if the viscosity number (IV) is higher than 0.7, the attaching property of the glue and the filling retention property after aging can be seriously problematic. The corresponding molecular weight ranges from 100000 to 2000000D, further optimized from 300000 to 1000000D, if less than 100000D, the cohesion after film formation is difficult to meet the requirements, and if more than 2000000D, the coating, fitting and filling properties are severely affected. The Tg of the adhesive film ranges from-60 ℃ to 0 ℃, more preferably from-50 ℃ to 0 ℃, and if the Tg is higher than 0 ℃, the adhesive property and filling property of the adhesive film are greatly affected.
As a specific embodiment, the OCA optical glue comprises the following raw materials in parts by weight: 100 parts of polymer, 30-75 parts of solvent, 0.01-5 parts of cross-linking agent, 0.01-5 parts of photoinitiator and 0.01-5 parts of antioxidant.
Solvents herein include, but are not limited to, ethyl acetate, butyl acetate, acetone, butanone, toluene, xylene, methanol, ethanol, isopropanol, butylene glycol, propylene glycol methyl ether, cyclohexane, petroleum ether. It is emphasized that the solvent component does not contain volatile highly toxic substances and halogens.
Crosslinking system: the crosslinking system herein includes both UV type crosslinking systems and thermal crosslinking systems. UV-type crosslinking agents include photoinitiators and crosslinking agents such as 1-hydroxycyclohexyl benzophenone, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 4-methylbenzophenone, methyl benzoate, 4-acryloxybenzophenone, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, 1, 6-hexanediol ethoxydiacrylate, pentaerythritol triacrylate, and the like; the thermal crosslinking system comprises: bayer L75, isocyanate curing agents L45 and D40, aziridine crosslinking agents CX-100, CX-100ZK-100, aziridine crosslinking agent XR-100, aziridine crosslinking agent GY-225, polyethylenimine crosslinking agents SaC-100, XC-203 and propylene imine trifunctional polyethylenimine PZ-28.
The crosslinking system can also select epoxy acrylate monomers as a crosslinking agent, wherein the epoxy acrylate monomers comprise one or more of tetrahydrofuran methacrylate, glycerol formal methacrylate, 2-acrylic acid (tetrahydro-2-furyl) methyl ester, (2-ethyl-2-methyl-1, 3-dioxypentyl-4-yl) acrylate, cyclotrimethylol propane methylacrylate and 3-ethyl-3-epoxypropyl (methyl) acrylate.
An antioxidant: antioxidants include conventional BHT (2, 6-di-tert-butyl-4-methylphenol), antioxidant SONGNOOX 1010, light stabilizer 384-2, antioxidant 1520L, etc. The antioxidant is used for enhancing the ageing resistance of the product.
In addition, tackifier components can be added: tackifiers include rosin resins, C5-C9 resins, terpene resins, and the like, which are used to enhance the cling and peel forces of the product.
As a specific embodiment, the branching monomer in the polymer is selected from multifunctional double bond acrylate monomers.
As a specific embodiment, the multifunctional double bond acrylate monomer includes, but is not limited to, one or more of trimethylolpropane tri (meth) acrylate, tripentaerythritol octaacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate.
Preferably, the polymer is polymerized from the following raw materials in parts by weight: 50-70 parts of low Tg long-chain branched (methyl) acrylate monomer, 15-30 parts of high Tg (methyl) acrylate monomer, 5-15 parts of hydroxyl (methyl) acrylate monomer, 15-20 parts of functional acrylate monomer and 0.1-2 parts of branched monomer.
The low Tg long chain branched (meth) acrylate monomers include, but are not limited to, one or more of isooctyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, isononyl acrylate, tridecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, isostearyl (meth) acrylate, lauryl acrylate, isodecyl acrylate.
The high Tg (meth) acrylate monomers include, but are not limited to, one or more of isobornyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl acrylate, 3, 5-trimethylcycloethyl acrylate, benzyl acrylate, isobornyl acrylate, 2-ethylhexyl methacrylate.
The hydroxyl group-containing (meth) acrylate monomers include, but are not limited to, one or more of 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, hydroxyethyl acrylate, glycidyl methacrylate.
The functional monomer includes, but is not limited to, one or more of dimethylaminoethyl methacrylate, N-methylolmethacrylamide, (meth) acrylamide, acryloylmorpholine, N-dimethylacrylamide.
Here, special types of acrylate monomers, such as polyether acrylates, isocyanate acrylates, reactive amine acrylates, urethane acrylates, etc., may also be added to the raw material components of the polymer. The amount of the acrylic acid ester of this particular type added is not more than 10 parts.
In addition, modified monomers such as acrylic acid, isocyanate, 2-isocyanatoethyl methacrylate, etc. may be added.
The invention further aims to provide an OCA optical adhesive film, which comprises a heavy release film layer, an adhesive film layer and a light release film layer from bottom to top, wherein the adhesive film layer is obtained by coating the high-filling OCA optical adhesive on a release surface of the heavy release film and baking, the OCA optical adhesive film has a deformation recovery rate of 55-85% after 1000s thixotropic and 1000s recovery under normal temperature and 0.1MPa, and preferably the deformation recovery rate of the OCA optical adhesive film is 70-80%. If the recovery rate of the sample after UV crosslinking is lower than 55%, the problem of glue overflow, poor reworkability, foaming and the like can be caused by the insufficient rebound resilience of the sample; if the recovery rate is greater than 85%, the sample is severely foamed back at the filling edge after aging.
The product structure of the invention includes but is not limited to: sandwich structure from bottom to top is heavy release film, glued membrane, light release film respectively. The thickness of the adhesive film is divided into a thin type and a thick type. The thickness is between 5 and 100 micrometers, and the thickness is larger than 100 micrometers, such as 150 micrometers, 175 micrometers and other common thicknesses; in addition, according to the application scene, other structural designs such as five-layer structures, co-extrusion structures and the like can be formed in the product.
The application scene of the product mainly comprises filling, bonding and protecting display components such as an optical glass cover plate, a polaroid and the like. Compared with the traditional OCA, the product of the scheme is more suitable for groove and hole structures with complex designs, and structural designs needing to balance flexibility and rigidity.
Preferably, when the thickness of the adhesive film layer is 100 micrometers, 180-degree peel strength of the OCA optical adhesive film relative to the back surface of glass, measured under the conditions that the temperature is 23 ℃, the adhesive film is attached on the glass surface for 1 minute and the stretching speed is 0.3 m/min, is between 11 and 17N/25.4 mm; under the same test conditions, when the thickness of the adhesive film layer is 150 micrometers, the 180-degree peeling strength of the OCA optical adhesive film relative to the back surface of glass is 17.0-21N/25.4 mm.
Preferably, when the thickness of the adhesive film layer is 100 micrometers, 180-degree peel strength of the OCA optical adhesive film measured at 23 ℃ under the conditions of being attached to the polarizer POL for 1 minute and the stretching speed of 0.3 m/min is between 17 and 19N/25.4mm relative to the back surface of the polarizer POL; under the same test conditions, when the thickness of the adhesive film layer is 150 micrometers, the 180-degree peeling strength of the OCA optical adhesive film relative to the back surface of the polarizer POL is 18.0-21N/25.4 mm.
If the peeling strength of the optical adhesive film is smaller than 10N/25.4mm, the peeling force is insufficient, and the bonding and adhesive properties are affected; if the diameter is more than 30N/25.4mm, the reworking is difficult, the release force is increased, and the problems of reverse release and the like are caused. Under the condition of meeting the above conditions, the product does not have strict range requirements on modulus.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the polymer adopted in the raw materials of the high-filling OCA optical glue disclosed by the invention has a weight average molecular weight of 100000-2000000 daltons, the glass transition temperature of the polymer is in the range of minus 60-0 ℃, the intrinsic viscosity of the polymer is in the range of 0.30-0.70, and the deformation recovery rate of the OCA optical glue film after 1000s thixotropic and 1000s recovery is between 55-85% under the conditions of normal temperature and 0.1MPa, so that the glue film achieves the industry high standard in performances of laminating, filling, transportation and storage, anti-foaming and the like, and is also suitable for filling large-depth and more complex designs such as hole filling, curved surfaces, flexible electronic equipment and other scenes.
Detailed Description
The technical scheme of the invention is further described below in conjunction with specific embodiments.
1. Preparation of glue
The preparation process of the glue comprises solvent method, bulk thermal polymerization, photopolymerization and emulsion polymerization. The following is exemplified by the solvent method:
1. the solvent glue formulation is shown in Table 1
TABLE 1
Wherein: s represents a sample; c represents a comparison
2 EHA-isooctyl acrylate; BA-n-butyl acrylate; 2 EHMA-2-ethylhexyl methacrylate; IBOA-isobornyl acrylate; 2 HEA-hydroxyethyl acrylate; 4 HBA-4-hydroxybutyl acrylate; ACMO-acryloylmorpholine; GMA-glycidyl methacrylate; NNDMA-N, N-dimethylacrylamide; ACM-acrylamide; PEMP-pentaerythritol tetrakis (3-mercapto acrylate); TMMP-trimethylolpropane tris (3-mercaptopropionate); PE-1-a secondary mercaptan of the type PE-1 manufactured by Showa Denko K.K.; IEM-2-isocyanatoethyl methacrylate; karenz MOI-Karenz MOI isocyanate, model number of Showa Denko K.K.; AA-acrylic acid; karenz MOI-EG-Japanese Showa Denko K.K. model Karenz MOI-EG isocyanate.
Polymerization process (S1)
Base monomer 1 (50 parts), base monomer 4 (20 parts), hydroxyl-containing monomer 1 (10 parts), functional monomer (20 parts), branching monomer (0.5 parts), modifying monomer (0.5 parts), and the solvent were mixed, and then added to the reaction vessel at a time in the form of 50 parts of solid content. Turning on a stirring paddle, introducing nitrogen, slowly heating to 59 ℃, and preserving heat for 1 hour;
adding a first initiator, controlling the temperature at 61 ℃ for reaction for 3 hours, observing the torque rising condition, and if no change exists, initiating failure, wherein additional initiator is needed to be added and the reaction time is prolonged; if the torque exceeds 120MN. M, the molecular weight adjustment may be out of control, and the reaction is stopped and the material is discharged;
then adding a second initiator, controlling the temperature at 61 ℃ for reaction for 3 hours, observing the torque rising condition and the heat release condition, and stopping the reaction and discharging if the torque rises to 300 MN.m;
adding a third initiator, controlling the temperature at 75 ℃ for reaction for 6 hours, and if torque rise still exists, adding an additional initiator and prolonging the reaction time to ensure that the residual monomer is less than 1.5%;
then oxygen/compressed air is introduced for 3 hours, residual free radicals are removed, the temperature is raised to 85 ℃, special monomers (10 parts) are added, an antioxidant and a solvent are reacted for 2 hours, and if torque rises at the moment, the reaction is stopped immediately to prevent gel;
and (5) discharging and packaging.
Wherein, the special monomer adopts polyethoxylated acrylate resin, the antioxidant adopts BHT, the solvent adopts ethyl acetate, and the initiator adopted in the method is azo-bis-isobutyronitrile.
Polymerization process (S2)
Base monomer 1 (30 parts), base monomer 2 (30 parts), base monomer 3 (10 parts), hydroxyl-containing monomer 1 (10 parts), functional monomer (20 parts), branching monomer (0.5 part) and modifying monomer (0.5 part), and after mixing the solvents, the mixture was added to the reaction vessel at a time in the form of 50 parts of solid content. The stirring paddle is turned on, nitrogen is introduced, and after the temperature is slowly raised to 58 ℃, the temperature is kept for 1 hour.
Adding a first initiator, controlling the temperature at 61 ℃ (not lower than 59 ℃ or higher than 63 ℃) for reacting for 5 hours, observing the torque rising condition, and if no change exists, initiating failure, and adding an additional initiator and prolonging the reaction time; if the torque exceeds 120mn.m, the molecular weight regulation may run out, and the reaction may be stopped and discharged.
The second initiator batch was added and the reaction was allowed to proceed for 5 hours at 61 degrees celsius (not lower than 59 or higher than 63 degrees celsius), the torque rise was observed, and the exotherm was observed, and if the torque rise was 300mn.m, the molecular weight could be out of control and the reaction was stopped and discharged.
And adding a third initiator, controlling the temperature at 75 ℃ (not lower than 73 ℃ or higher than 78 ℃) and reacting for 6 hours, and if the torque is still increased, adding an additional initiator and prolonging the reaction time to ensure that the residual monomer is less than 1.5%.
Oxygen/compressed air was introduced for 2 hours to remove residual free radicals. Heating to 85 ℃, adding special monomer (8 parts), antioxidant and solvent, and reacting for 4 hours. If there is a torque rise at this time, the reaction should be stopped immediately to prevent gelation.
And (5) discharging and packaging.
Wherein, the special monomer adopts polyethoxylated acrylate resin, the antioxidant adopts BHT, the solvent adopts ethyl acetate, and the initiator adopted in the method is azo-bis-isobutyronitrile.
Polymerization process (S3)
Base monomer 1 (60 parts) base monomer 3 (10 parts), hydroxyl-containing monomer 2 (15 parts), functional monomer (15 parts), branching monomer (0.5 parts), modified monomer (0.5 parts), and the solvent was mixed, and then added to the reaction vessel at a time in the form of 50% solids. The stirring paddle is turned on, nitrogen is introduced, and after the temperature is slowly raised to 59 ℃, the temperature is kept for 1 hour.
Adding a first initiator, controlling the temperature at 61 ℃ (not lower than 59 ℃ or higher than 63 ℃) for reaction for 3 hours, observing the torque rising condition, if no change exists, initiating failure, adding an additional initiator and prolonging the reaction time; if the torque exceeds 120mn.m, the molecular weight regulation may run out, and the reaction may be stopped and discharged.
The second initiator batch was added and the reaction was allowed to proceed for 3 hours at 61 degrees celsius (not lower than 59 or higher than 63 degrees celsius), the torque rise was observed, and the exotherm was observed, and if the torque rise was 300mn.m, the molecular weight could be out of control and the reaction was stopped and discharged.
And adding a third initiator, controlling the temperature at 75 ℃ (not lower than 73 ℃ or higher than 78 ℃) and reacting for 6 hours, and if the torque is still increased, adding an additional initiator and prolonging the reaction time to ensure that the residual monomer is less than 1.5%.
Oxygen/compressed air was introduced for 3 hours to remove residual free radicals. Heating to 85 ℃, adding special monomer (10 parts), antioxidant and solvent, and reacting for 2 hours. If there is a torque rise at this time, the reaction should be stopped immediately to prevent gelation.
And (5) discharging and packaging.
Wherein the special monomer is isocyanate acrylic ester, the antioxidant is antioxidant SONGNOOX 1010, and the solvent is ethanol.
Polymerization process (S4)
Base monomer 1 (40 parts), base monomer 4 (25 parts), hydroxyl-containing monomer 2 (5 parts), functional monomer (20 parts), branching monomer (0.6 parts), functional monomer (0.3 parts), and the solvent were mixed, and then added to the reaction vessel at a time in the form of 50% solids. The stirring paddle is turned on, nitrogen is introduced, and after the temperature is slowly raised to 59 ℃, the temperature is kept for 1 hour.
Adding a first initiator, controlling the temperature at 62 ℃ which can not be lower than 60 ℃ or higher than 64 ℃ for 4 hours, observing the torque rising condition, if no change exists, initiating failure, adding an additional initiator and prolonging the reaction time; if the torque exceeds 120mn.m, the molecular weight regulation may run out, and the reaction may be stopped and discharged.
The second initiator is added, the temperature is controlled at 62 ℃ and can not be lower than 60 ℃ or higher than 64 ℃, the reaction is carried out for 4 hours, the torque rising condition and the heat release condition are observed, if the torque rises to 300MN. M, the molecular weight can be out of control, and the reaction and discharging are stopped.
And adding a third initiator, controlling the temperature at 78 ℃ (not lower than 76 ℃ or higher than 80 ℃) for reaction for 5 hours, and if the torque is still increased, adding an additional initiator and prolonging the reaction time to ensure that the residual monomer is less than 1.5%.
Oxygen/compressed air was introduced for 3 hours to remove residual free radicals. Heating to 90 ℃, adding special monomer, antioxidant and solvent, and reacting for 2 hours. If there is a torque rise at this time, the reaction should be stopped immediately to prevent gelation.
And (5) discharging and packaging.
Wherein the special monomer is isocyanate acrylic ester, the antioxidant is antioxidant SONGNOOX 1010, and the solvent is ethanol.
2. Performance testing and characterization
Sample example
TABLE 2
C1 C2 is a commercially available head OCA bid for high filling, all 150 μm thick.
Preparation of adhesive films of sample numbers S1-150 to S4-100, comparative examples C1-150 and C2-150
Taking sample number S1-150 as an example, mixing 100 parts of polymer, 0.1 part of photoinitiator IRGCURE 184, 1 part of antioxidant and 1 part of petroleum resin (ECR 1401 manufactured by Exxon Mobil chemical industry), uniformly stirring, standing for defoaming to obtain OCA optical glue, coating the glue on a heavy release film, baking for 5min at 120 ℃, and then attaching the glue to a light release film to form a three-layer structure of the heavy release film layer, the glue film and the light release film layer from bottom to top.
The above samples and comparative samples were subjected to performance tests, the test items are as follows, and the instruments used for the tests are shown in Table 3:
1) Optical properties: including light transmittance, L, a, b, haze, refractive index.
2) Mechanical properties: the method comprises 180-degree stripping force of the glass surface, 180-degree stripping force of the polarizer surface, storage modulus, loss modulus and a positive cutting angle at different temperatures, and a release force range of light and heavy sides.
3) Filling effect and ageing resistance: including the fit, die-cut, reworkability (film uncovering), cold-release, hot-release, deformation recovery.
And (3) heat disassembly: and transferring the adhesive film with the width of 1inch and without illumination to a clean and smooth glass surface in a constant-temperature laboratory at 23 ℃, and re-lifting the adhesive film by hands after lamination, wherein if the adhesive film is not remained and the solvent is not used, all the adhesive films can be completely removed, the adhesive film passes, and otherwise, the adhesive film does not pass.
General evaluation of aging experiments: after aging, the sample has no bubble return, no yellowing, no whitening, no warping/gumming, and the sample passes; any of the above defects is not passed.
TABLE 3 Table 3
The test results were as follows:
optical Properties
TABLE 4 Table 4
Mechanical properties
TABLE 5
Die cutting, laminating and ageing properties
TABLE 6
From tables 4, 5 and 6, it can be seen that, compared with the existing head bidding products, the optical performance, the mechanical performance, the reworkability and the aging resistance are equal to or better than the existing head bidding products, especially the reworkability after 200 rounds of high and low temperature circulation is obviously better than the existing products.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (8)
1. The OCA optical glue with high filling property is characterized in that the OCA optical glue comprises a polymer, at least two components of a solvent, a cross-linking agent, a photoinitiator and an antioxidant, wherein the polymer has a weight average molecular weight of 100000-2000000 daltons and a glass transition temperature of-60-0 ℃, the intrinsic viscosity of the polymer is 0.30-0.70, and the polymer is polymerized from the following raw materials in parts by weight: 40-80 parts of low Tg long-chain branched (methyl) acrylate monomer, 10-40 parts of high Tg (methyl) acrylate monomer, 1-15 parts of hydroxyl (methyl) acrylate monomer, 1-20 parts of functional acrylate monomer and 0.1-5 parts of branching monomer, wherein the branching monomer is selected from any one of pentaerythritol tetra (3-mercapto acrylate), trimethylolpropane tri (3-mercapto propionate) and secondary mercaptan with the model PE-1 manufactured by Japanese Showa electric Co.
2. The high-filling OCA optical glue according to claim 1, wherein the polymer has a weight average molecular weight of 300000-1500000 daltons, a glass transition temperature in the range of-50-0 ℃ and an intrinsic viscosity in the range of 0.40-0.50.
3. The high-filling-property OCA optical glue as claimed in claim 1, wherein the raw materials of the OCA optical glue comprise, by weight: 100 parts of polymer, 30-75 parts of solvent, 0.01-5 parts of cross-linking agent, 0.01-5 parts of photoinitiator and 0.01-5 parts of antioxidant.
4. The high-filling OCA optical glue according to claim 1, wherein the polymer is obtained by polymerizing the following raw materials in parts by weight: 50-70 parts of low Tg long-chain branched (methyl) acrylate monomer, 15-30 parts of high Tg (methyl) acrylate monomer, 5-15 parts of hydroxyl (methyl) acrylate monomer, 15-20 parts of functional acrylate monomer and 0.1-2 parts of branched monomer.
5. An OCA optical adhesive film comprising a heavy release film layer, an adhesive film layer and a light release film layer from bottom to top, wherein the adhesive film layer is obtained by coating the high-filling OCA optical adhesive glue as set forth in any one of claims 1 to 4 on a release surface of a heavy release film and baking the adhesive film, and is characterized in that the OCA optical adhesive film has a deformation recovery rate of 55-85% after 1000s thixotropic and 1000s recovery at normal temperature and 0.1 MPa.
6. The OCA optical film of claim 5, wherein the OCA optical film has a deformation recovery of between 70% and 80%.
7. The OCA optical adhesive film according to claim 5, wherein 180 degree peel strength of the OCA optical adhesive film against the back surface of glass measured at 23 ℃ for 1 minute attached to the glass surface at a stretching speed of 0.3 m/min is between 11 and 17N/25.4mm when the thickness of the adhesive film layer is 100 μm; under the same test conditions, when the thickness of the adhesive film layer is 150 micrometers, the 180-degree peeling strength of the OCA optical adhesive film relative to the back surface of glass is 17.0-21N/25.4 mm.
8. The OCA optical film of claim 5, wherein when the film layer thickness is 100 micrometers, the 180 degree peel strength of the OCA optical film against the back side of the polarizer POL measured at 23 ℃ for 1 minute at a stretching speed of 0.3 m/min is between 17 and 19N/25.4 mm; under the same test conditions, when the thickness of the adhesive film layer is 150 micrometers, the 180-degree peeling strength of the OCA optical adhesive film relative to the back surface of the polarizer POL is 18.0-21N/25.4 mm.
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