CN114214006A - High-filling-property OCA (optical clear adhesive) optical glue and OCA optical adhesive film - Google Patents
High-filling-property OCA (optical clear adhesive) optical glue and OCA optical adhesive film Download PDFInfo
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- CN114214006A CN114214006A CN202111634060.5A CN202111634060A CN114214006A CN 114214006 A CN114214006 A CN 114214006A CN 202111634060 A CN202111634060 A CN 202111634060A CN 114214006 A CN114214006 A CN 114214006A
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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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- 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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- 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
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- 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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Abstract
The invention discloses high-filling OCA optical glue and an OCA optical adhesive 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 within 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-containing (methyl) acrylate monomer, 1-20 parts of functional acrylate monomer and 0.1-5 parts of branched monomer. The prepared adhesive film reaches the high industrial standard in the performances of laminating, filling, transporting and storing, anti-bubble inhibiting 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-property OCA (optically clear adhesive) optical glue and an OCA optical adhesive film.
Background
Optical Clear Adhesive (OCA) is a novel material which is applied to display equipment mainly using liquid crystal and has the composite functions of light transmission, light uniformization, display enhancement, protection and the like. The broad OCAs can be further classified into OCR (optically clear resin), OCA (optically clear adhesive film) and LOCA (i.e., liquid optical adhesive-currently tending to ink jet printing OCA) according to product morphology. The earliest OCA was proposed by Hitachi chemical industry in the form of OCR, and developed by Minnesota mining and manufacturing (3M) and Mitsubishi chemical company in Japan to become the mainstream OCA film products in the market (patent similar to the present invention include WO2011129200A1, US20030064188A1, WO2009131792A1, US5520978A, and CN 101998982A). As a basic requirement, an OCA adhesive film must be absolutely clean and stable in the manufacturing process, the surface of a base material must be fully soaked in a short time and all air must be exhausted in the process of bonding, the OCA must have good bonding capacity for the base material with different surface energies at two sides, and the OCA must be capable of resisting environmental comprehensive factors such as long-time UV, water vapor, heat, temperature change and the like in the aging process.
China is the largest electronic product production area in the world at present, but the supply chain of OCA is monopolized by foreign resources. According to the market conservation estimation, the market share of only two companies, namely 3M and Mitsubishi, in China accounts for more than 90%. The reasons for monopolizing the material are complex. Firstly, the OCA is different from a common adhesive, has extremely high requirements on the whole set of manufacturing process except the uniqueness of a formula, and the product yield and the effect stability before and after use directly determine the production cost, the performance and the market competitiveness of related electronic products; furthermore, a small number of companies invest a large amount of time and cost in the development of the OCA, related technologies are monopolized by the OCA, and new domestic competitors lack autonomous intellectual property protection on the premise of no autonomous IP support, so that subsequent long-term innovation and development are influenced.
On the other hand, the demand gap for OCA in the related industries is enormous. With the rapid iteration and derivation of electronic products, the demand for OCA performance tends to become integrated and superior. This results in the inability of conventional OCAs to meet new requirements; meanwhile, as China becomes the first electronic product research and development and production country in the world, the demand of OCA shows blowout-type growth. The independent research and development, iteration and production capacity of the OCA product become one of material bottlenecks which restrict the development of the electronic technology industry.
Under the background, in combination with specific industrial requirements, a high-performance OCA with independent intellectual property rights is urgently needed to be developed, so that the product not only meets the basic performance requirements of the OCA, but also has transportation stability, flexible matching performance of a fitting process, excellent filling performance, stability of a production process and certain universality.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide OCA optical glue with high filling property.
In order to achieve the purpose, the invention adopts the technical scheme that: 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 dalton (D for short), the glass transition temperature of the polymer is in the range of-60-0 ℃, the intrinsic viscosity of the polymer is in the range of 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-containing (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 a product is required to be between 0.3 and 0.7, if the characteristic viscosity number (IV) is less than 0.3, the cohesive force of the glue can cause serious problems, and if the characteristic viscosity number (IV) is more than 0.7, the attaching performance of the glue and the retention performance of filling after aging can cause serious problems. The corresponding molecular weight range is 100000-2000000D, and further optimized to 300000-1000000D, if less than 100000D, the cohesion after film formation is difficult to satisfy, if more than 2000000D, the coating, bonding and filling properties are seriously affected. The Tg range of the adhesive film is-60-0 ℃, more preferably-50-0 ℃, and if the Tg range is higher than 0 ℃, the bonding property and the filling property of the product are greatly influenced.
As a specific implementation mode, 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.
Solvents herein include, but are not limited to, ethyl acetate, butyl acetate, acetone, butanone, toluene, xylene, methanol, ethanol, isopropanol, butanediol, propylene glycol methyl ether, cyclohexane, petroleum ether. It is emphasized that the solvent component does not contain volatile highly toxic substances and halogens.
A crosslinking system: the crosslinking system herein includes both a UV type crosslinking system and a thermal crosslinking system. Crosslinking agents of the UV type include photoinitiators and crosslinking agents such as 1-hydroxycyclohexyl benzophenone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 4-methylbenzophenone, methyl benzoylformate, 4-acryloxybenzophenone, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, 1, 6-hexanediol ethoxylate diacrylate, pentaerythritol triacrylate, etc.; the thermal crosslinking system comprises: bayer L75, isocyanate curing agent L45, D40, aziridine crosslinking agent CX-100, CX-100ZK-100, aziridine crosslinking agent XR-100, aziridine crosslinking agent GY-225, polyaziridine crosslinking agent Sac-100, XC-203, propyleneimine trifunctional polyaziridine 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 but not limited to tetrahydrofuran methacrylate, glycerol formal methacrylate, 2-acrylic acid (tetrahydro-2-furyl) methyl ester, (2-ethyl-2-methyl-1, 3-dioxopentyl-4-yl) acrylate, cyclotrimethylolpropane formal acrylate and 3-ethyl-3-epoxypropyl (methyl) methyl acrylate.
Antioxidant: the antioxidant comprises BHT (2, 6-di-tert-butyl-4-methylphenol), SONGNOOX 1010, light stabilizer 384-2, antioxidant 1520L and the like which are commonly used. The antioxidant is used for enhancing the aging resistance of the product.
In addition, a tackifier component can be added: the tackifier comprises rosin resin, C5-C9 resin, terpene resin and the like, and is used for enhancing the attaching performance and the stripping force 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 obtained by polymerizing raw materials comprising the following components 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-containing (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 monomer includes, but is not limited to, one or more of isobornyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl acrylate, 3, 5-trimethylhydroxyethyl acrylate, benzyl acrylate, isobornyl acrylate, 2-ethylhexyl methacrylate.
The hydroxyl group-containing (meth) acrylate monomer includes, but is not limited to, one or more of 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, hydroxyethyl acrylate, and glycidyl methacrylate.
The functional monomer includes but is not limited to one or more of dimethylaminoethyl methacrylate, N-methylol methacrylamide, (meth) acrylamide, acryloyl morpholine, N-dimethyl acrylamide.
Here, special types of acrylate monomers such as polyether acrylates, isocyanate acrylates, reactive amine acrylates, urethane acrylates, and the like may also be added to the raw material components of the polymer. The amount of acrylate of this particular type is not more than 10 parts.
In addition, modifying monomers such as acrylic acid, isocyanate, 2-isocyanatoethyl methacrylate and the like can be added.
The invention also 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 deformation recovery rate of the OCA optical adhesive film after 1000s thixotropy and 1000s recovery is 55-85% at 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 rebound resilience of the sample is insufficient, so that the problems of glue overflow, poor reworkability, foaming and the like can be caused; if the recovery rate is more than 85%, the sample is seriously bubble-returned at the filling edge after aging.
Product structures of the present invention include, but are not limited to: the sandwich structure is respectively a heavy release film, an adhesive film and a light release film from bottom to top. The thickness of the glue film is divided into thin type and thick type. The thin type is between 5 and 100 micrometers, the thick type is more than 100 micrometers, such as the common thickness of 150 and 175 micrometers; in addition, according to application scenes, the product may have five-layer structures, co-extrusion structures and other structural designs.
The application scenes of the product are mainly filling, bonding and protecting of 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 a groove and hole structure with complex design and a structural design which needs balancing flexibility and rigidity.
Preferably, when the thickness of the adhesive film layer is 100 microns, the 180-degree peel strength of the OCA optical adhesive film relative to the back surface of the glass, which is measured under the conditions that the OCA optical adhesive film is attached to the glass surface for 1 minute at the temperature of 23 ℃ 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 microns, the 180-degree peel strength of the OCA optical adhesive film relative to the back surface of the glass is 17.0-21N/25.4 mm.
Preferably, when the thickness of the adhesive film layer is 100 micrometers, the 180-degree peel strength of the OCA optical adhesive film relative to the back surface of the polarizer POL, which is measured under the conditions that the adhesive film layer is attached to the polarizer POL at the temperature of 23 ℃ for 1 minute and the stretching speed is 0.3 m/min, is between 17 and 19N/25.4 mm; under the same test condition, when the thickness of the adhesive film layer is 150 microns, the 180-degree peel 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 less than 10N/25.4mm, the peeling force is insufficient, and the bonding and adhesive properties are affected; if the thickness is more than 30N/25.4mm, the problems of difficult rework, increased release force, reverse release and the like can be caused. Under the condition of meeting the condition ranges, the product does not have strict range requirements on the 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 has the weight average molecular weight of 100000-.
Detailed Description
The technical solution of the present invention is further illustrated below with reference to specific examples.
Firstly, preparation of glue
The preparation process of the glue comprises a solvent method, bulk thermal polymerization, photopolymerization and emulsion polymerization. The following are illustrated by solvent methods:
1. the solvent glue formula is shown in Table 1
TABLE 1
Wherein: s represents a sample; c represents comparison
2 EHA-isooctyl acrylate; BA-n-butyl acrylate; 2 EHMA-2-ethylhexyl methacrylate; IBOA-isobornyl acrylate; 2 HEA-hydroxyethyl acrylate; 4 HBA-4-hydroxybutylacrylate; ACMO-acryloylmorpholine; GMA-glycidyl methacrylate; NNDMA-N, N-dimethylacrylamide; ACM-acrylamide; PEMP-pentaerythritol tetrakis (3-mercaptoacrylate); TMMP-trimethylolpropane tris (3-mercaptopropionate); PE-1-a secondary thiol of type PE-1 from Showa Denko K.K.; IEM-2-isocyanatoethyl methacrylate; karenz MOI-a model number of Karenz MOI isocyanate from Showa Denko K.K.; AA-acrylic acid; karenz MOI-EG-manufactured by Karenz MOI-EG corporation of Japan is Karenz MOI-EG isocyanate.
Polymerization process (S1)
After mixing a solvent with 1(50 parts) of a basic monomer, 4(20 parts) of a basic monomer, 1(10 parts) of a hydroxyl group-containing monomer, 20 parts of a functional monomer, 0.5 part of a branched monomer and 0.5 part of a modifying monomer, the mixture was added to a reaction kettle at a time in the form of 50 parts of solid content. Opening a stirring paddle, introducing nitrogen, slowly heating to 59 ℃, and then preserving heat for 1 hour;
adding a first batch of initiator, controlling the temperature at 61 ℃, reacting for 3 hours, observing the torque rise condition, and if the torque rise condition is not changed, initiating failure needs to be carried out, and additional initiator needs to be added and the reaction time is prolonged; if the torque exceeds 120MN.m, the molecular weight regulation is out of control, and the reaction is stopped and the material is discharged;
then adding a second batch of initiator, controlling the temperature at 61 ℃, reacting for 3 hours, observing the torque rising condition and the heat release condition, if the torque rises to 300MN.m, the molecular weight is out of control, stopping the reaction and discharging;
adding a third batch of initiator, controlling the temperature at 75 ℃, reacting for 6 hours, if the torque rises, adding an additional initiator and prolonging the reaction time to ensure that the residual monomer is less than 1.5%;
then introducing oxygen/compressed air for 3 hours, removing residual free radicals, heating to 85 ℃, adding special monomers (10 parts), an antioxidant and a solvent, reacting for 2 hours, and if the torque rises, immediately stopping the reaction to prevent gelation;
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 azobisisobutyronitrile.
Polymerization process (S2)
The preparation method comprises the following steps of mixing a base monomer 1(30 parts), a base monomer 2(30 parts), a base monomer 3(10 parts), a hydroxyl-containing monomer 1(10 parts), a functional monomer (20 parts), a branched monomer (0.5 part) and a modified monomer (0.5 part) with a solvent, and adding the mixture into a reaction kettle at one time in a solid content of 50 parts. And opening the stirring paddle, introducing nitrogen, slowly heating to 58 ℃, and then preserving heat for 1 hour.
Adding a first batch of initiator, controlling the temperature to be 61 ℃ (the temperature can not be lower than 59 ℃ or higher than 63 ℃), reacting for 5 hours, observing the torque rise condition, if the torque rise condition is not changed, initiating failure occurs, and adding additional initiator and prolonging the reaction time; if the torque exceeds 120MN.m, the molecular weight regulation may be out of control, and the reaction needs to be stopped and the material is discharged.
Adding a second batch of initiator, controlling the temperature at 61 ℃ (not lower than 59 ℃ or higher than 63 ℃), reacting for 5 hours, observing the torque rise condition and the heat release condition, and if the torque rises to 300MN.m, the molecular weight can be out of control, stopping the reaction and discharging.
Adding a third batch of initiator, controlling the temperature to be 75 ℃ (the temperature can not be lower than 73 ℃ or higher than 78 ℃), reacting for 6 hours, and if the torque rises, adding additional initiator and prolonging the reaction time to ensure that the residual monomer is less than 1.5%.
Oxygen/compressed air was passed in for 2 hours to remove residual free radicals. Heating to 85 ℃, adding the special monomer (8 parts), the antioxidant and the solvent, and reacting for 4 hours. If the torque rises at this time, the reaction should be stopped immediately to prevent gelation.
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 azobisisobutyronitrile.
Polymerization process (S3)
A basic monomer 1(60 parts), a basic monomer 3(10 parts), a hydroxyl group-containing monomer 2(15 parts), a functional monomer (15 parts), a branched monomer (0.5 part), and a modifying monomer (0.5 part) were mixed with a solvent and added to a reaction vessel at a time in the form of 50% solid content. And opening the stirring paddle, introducing nitrogen, slowly heating to 59 ℃, and then preserving heat for 1 hour.
Adding a first batch of initiator, controlling the temperature to be 61 ℃ (the temperature can not be lower than 59 ℃ or higher than 63 ℃), reacting for 3 hours, observing the torque rise condition, if the torque rise condition is not changed, initiating failure occurs, and adding additional initiator and prolonging the reaction time; if the torque exceeds 120MN.m, the molecular weight regulation may be out of control, and the reaction needs to be stopped and the material is discharged.
Adding a second batch of initiator, controlling the temperature at 61 ℃ (not lower than 59 ℃ or higher than 63 ℃), reacting for 3 hours, observing the torque rise condition and the heat release condition, and if the torque rises to 300MN.m, the molecular weight can be out of control, stopping the reaction and discharging.
Adding a third batch of initiator, controlling the temperature to be 75 ℃ (the temperature can not be lower than 73 ℃ or higher than 78 ℃), reacting for 6 hours, and if the torque rises, adding additional initiator and prolonging the reaction time to ensure that the residual monomer is less than 1.5%.
Oxygen/compressed air was bubbled for 3 hours to remove residual free radicals. Heating to 85 ℃, adding the special monomer (10 parts), the antioxidant and the solvent, and reacting for 2 hours. If the torque rises at this time, the reaction should be stopped immediately to prevent gelation.
Discharging and packaging.
Wherein the special monomer is isocyanate acrylate, the antioxidant is antioxidant SONGNOOX 1010, and the solvent is ethanol.
Polymerization process (S4)
A basic monomer 1(40 parts), a basic monomer 4(25 parts), a hydroxyl group-containing monomer 2(5 parts), a functional monomer (20 parts), a branched monomer (0.6 part), and a functional monomer (0.3 part) were mixed with a solvent and added to a reaction vessel at a time in the form of 50% solid content. And opening the stirring paddle, introducing nitrogen, slowly heating to 59 ℃, and then preserving heat for 1 hour.
Adding a first batch of initiator, controlling the temperature to be 62 ℃ (not lower than 60 ℃ or higher than 64 ℃), reacting for 4 hours, observing the torque rise condition, and if the torque rise condition is not changed, initiating failure occurs, and adding additional initiator and prolonging the reaction time; if the torque exceeds 120MN.m, the molecular weight regulation may be out of control, and the reaction needs to be stopped and the material is discharged.
Adding a second batch of initiator, controlling the temperature at 62 ℃ (not lower than 60 ℃ or higher than 64 ℃), reacting for 4 hours, observing the torque rise condition and the heat release condition, and if the torque rises to 300MN.m, the molecular weight can be out of control, stopping the reaction and discharging.
Adding a third batch of initiator, controlling the temperature to be 78 ℃ (the temperature can not be lower than 76 ℃ or higher than 80 ℃), reacting for 5 hours, and if the torque is still increased, adding additional initiator and prolonging the reaction time to ensure that the residual monomer is less than 1.5%.
Oxygen/compressed air was bubbled for 3 hours to remove residual free radicals. Heating to 90 ℃, adding the special monomer, the antioxidant and the solvent, and reacting for 2 hours. If the torque rises at this time, the reaction should be stopped immediately to prevent gelation.
Discharging and packaging.
Wherein the special monomer is isocyanate acrylate, the antioxidant is antioxidant SONGNOOX 1010, and the solvent is ethanol.
Second, performance testing and characterization
Sample examples
TABLE 2
C1 and C2 are the same high-filling head OCA competitive products on the market, and the thicknesses of the products are 150 mu m.
Preparation of sample numbers S1-150-S4-100, comparative examples C1-150 and C2-150 glue films
Taking sample number S1-150 as an example, 100 parts of polymer, 0.1 part of photoinitiator IRGCURE 184, 1 part of antioxidant and 1 part of petroleum resin (ECR 1401 model manufactured by Exxon Mobil chemical industry) are mixed and stirred uniformly, then the mixture is kept stand and defoamed to obtain OCA optical glue, then the OCA optical glue is coated on a heavy release film, the mixture is baked for 5min at the temperature of 120 ℃, and then the glue is attached to a light release film to form a three-layer structure which is a heavy release film layer, a glue film and a light release film layer from bottom to top in sequence.
The performance of the above samples and the comparative samples were tested according to the following test items, and the instruments used in 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 polaroid surface, storage modulus, loss modulus and tangent angle at different temperatures, and release force ranges of light side and heavy side.
3) Filling effect and aging resistance: including conformability, cross cutting nature, reworkability (uncovering the membrane nature), cold tearing nature, hot tearing nature, deformation recovery ability.
Hot dismantling: in a constant temperature laboratory at 23 ℃, 1inch wide non-illuminated adhesive film is transferred to the surface of clean and smooth glass, after the adhesive film is attached, the adhesive film is lifted up again by hand, if all the adhesive films can be completely removed without residual adhesive film or solvent, the adhesive film passes through, otherwise, the adhesive film does not pass through.
General evaluation of aging test: after aging, the sample has no bubble return, no yellowing, no whitening and no warping/glue opening, and the sample passes; if any of the above defects are present, the failure is detected.
TABLE 3
The test results were as follows:
optical Properties
TABLE 4
Mechanical properties
TABLE 5
Die cutting, laminating and aging properties
TABLE 6
From tables 4, 5 and 6, it can be seen that, compared with the existing head competitors, the optical performance, the mechanical performance, the reworking performance and the aging resistance are equal to or better than those of the existing head competitors, and particularly, the reworking performance after 200 rounds of high and low temperature cycles is obviously better than that of the existing products.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. The high-filling OCA optical cement is characterized in that the raw materials of the OCA optical cement 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-containing (methyl) acrylate monomer, 1-20 parts of functional acrylate monomer and 0.1-5 parts of branched monomer.
2. The highly filled OCA optical cement according to claim 1, wherein said polymer has a weight average molecular weight of 300000-1500000 dalton, 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 according to claim 1, wherein the raw materials of the OCA optical glue comprise, 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.
4. The highly filled OCA optical cement according to claim 1, wherein a multifunctional double bond acrylate monomer is selected as a branching monomer in the polymer.
5. The high-filling OCA optical cement as claimed in claim 4, wherein said 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.
6. The high-filling-property OCA optical glue according to claim 1, wherein the polymer is obtained by polymerizing raw materials comprising the following components 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-containing (methyl) acrylate monomer, 15-20 parts of functional acrylate monomer and 0.1-2 parts of branched monomer.
7. An OCA optical adhesive film 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 of any one of claims 1 to 6 on a release surface of the heavy release film and baking the coating, and the OCA optical adhesive film is characterized in that the deformation recovery rate of the OCA optical adhesive film after 1000s thixotropy and 1000s recovery is 55-85% at normal temperature and 0.1MPa, and preferably the deformation recovery rate of the OCA optical adhesive film is 70-80%.
8. The OCA optical adhesive film according to claim 7, wherein when the thickness of the adhesive film layer is 100 μm, the 180-degree peel strength of the OCA optical adhesive film with respect to the back surface of the glass, measured under the conditions of 1 minute of adhesion to the glass surface at 23 ℃ and 0.3 m/min of stretching speed, is between 11 and 17N/25.4 mm; under the same test conditions, when the thickness of the adhesive film layer is 150 microns, the 180-degree peel strength of the OCA optical adhesive film relative to the back surface of the glass is 17.0-21N/25.4 mm.
9. The OCA optical adhesive film according to claim 7, wherein when the thickness of the adhesive film is 100 μm, the 180-degree peel strength of the OCA optical adhesive film relative to the back surface of the polarizer POL, measured under the conditions of 1 minute of adhesion to the polarizer POL at 23 ℃ and 0.3 m/min of stretching speed, is 17-19N/25.4 mm; under the same test condition, when the thickness of the adhesive film layer is 150 microns, the 180-degree peel 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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| CN117025138A (en) * | 2023-10-08 | 2023-11-10 | 苏州凡赛特材料科技有限公司 | Adhesive and adhesive film for assembling polarizing materials in display module |
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