WO2023116494A1 - 胶粘剂组合物及其制备方法、光学胶膜及其应用 - Google Patents

胶粘剂组合物及其制备方法、光学胶膜及其应用 Download PDF

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WO2023116494A1
WO2023116494A1 PCT/CN2022/138515 CN2022138515W WO2023116494A1 WO 2023116494 A1 WO2023116494 A1 WO 2023116494A1 CN 2022138515 W CN2022138515 W CN 2022138515W WO 2023116494 A1 WO2023116494 A1 WO 2023116494A1
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groups
formula
modified polymer
group
boron
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PCT/CN2022/138515
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English (en)
French (fr)
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赵迎波
龙浩晖
李健辉
方建平
肖甜
吴锦荣
兀琪
熊慧
黄悦
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华为技术有限公司
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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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C09J183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • 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
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

Definitions

  • the present application relates to an adhesive composition, a preparation method of the adhesive composition, an optical adhesive film prepared from the adhesive composition, a folding screen containing the optical adhesive film, and an electronic device containing the optical adhesive film or the folding screen .
  • Foldable screen electronic devices are more and more popular because of their foldable screens, which bring brand-new visual experience and convenience to users in fields such as reading, gaming and office work.
  • the structure of the folding screen mainly includes a panel and a cover plate on the front of the panel, wherein the base material of the cover plate is an organic film material with excellent bendability, such as polyimide film (PI), polyethylene terephthalate Ethylene glycol formate film (PET), etc.
  • PI polyimide film
  • PET polyethylene terephthalate Ethylene glycol formate film
  • OCA Optical Clear Adhesive
  • LOCA Liquid Optical Clear Adhesive
  • the existing OCA/LOCA systems are acrylic polymer systems or silicone polymer systems, and the elastic modulus is too low, about 10Kpa to 500Kpa. Good resistance to external impact, it is easy to deform, so that a strong external force acts on the OCA/LOCA film layer, but the existing OCA/LOCA has poor impact resistance, and the impact energy cannot be absorbed or dissipated, and then transmitted to the panel Lead to failure phenomena such as black spots or broken bright spots on the panel.
  • the first aspect of the embodiment of the present application provides an adhesive composition
  • the adhesive composition includes an adhesive matrix and a modified polymer, wherein the main chain of the modified polymer contains boron-oxygen coordination and/or The boron-oxygen coordination bond is connected, and the terminal group and/or side chain of the modified polymer contains at least one of hydroxyl group, acrylate group and vinyl group.
  • a boron-oxygen coordination bond and a boron-oxygen coordination bond is introduced into the main molecular chain of the modified polymer of the present application. Due to the boron-oxygen coordination bond or the boron-oxygen coordination bond under the action of low strain rate, there is enough time for the fracture behavior to ensure that the molecular chain is flexible and bendable at low modulus; at high strain Under the effect of speed, the time scale of the molecular chain movement is much smaller than the time for the breaking of the boron-oxygen coordination bond or the boron-oxygen coordination bond, and the unbroken boron-oxygen coordination bond or the boron-oxygen coordination bond hinders the molecular The movement of the chain makes it difficult for the molecular chain to move sufficiently to untangle, and it shows the characteristics of rigidity and elasticity macroscopically.
  • the unique fracture and bonding behavior of the boron-oxygen coordination bond or above the boron-oxygen coordination bond enables the adhesive composition to have excellent energy absorption and impact resistance properties under the premise of ensuring the bonding strength, and can absorb the shock generated by external forces. Ability to resist the impact of impact on the panel.
  • active groups such as terminal hydroxyl groups, terminal acrylate groups, and terminal vinyl groups into the terminal groups of the modified polymer, it is beneficial to have a crosslinking reaction with the adhesive matrix or acrylate monomers.
  • the structural formula of the modified polymer is formula (1) - formula (2), and the structure of formula (1) - formula (2) is as follows:
  • R 1 and R 2 in formula (1)-formula (2) are independently selected from free alkyl groups, free alkoxy groups, alkenyl groups, cycloalkyl groups and aryl groups groups in the group consisting of;
  • the adhesive matrix includes at least one of silicone resin and epoxy resin.
  • the siloxane resin includes polydiorganosiloxane terminated by at least one of alkoxy, acyloxy, and ketoxime groups, and the polydiorganosiloxane
  • Each organic group in the siloxane is independently selected from any one of free alkyl groups, free alkoxy groups, alkenyl groups, cyclohydrocarbyl groups and aryl groups;
  • the epoxy resin includes at least one of bisphenol A type epoxy resin and bisphenol F type epoxy resin.
  • the ratio of the adhesive matrix to the modified polymer is (10-80): (50-90) or (10-30): (50- 90).
  • the structural formula of the modified polymer is formula (3) - formula (6), and the structure of formula (3) - formula (6) is as follows:
  • R 1 and R 2 in formula (3)-formula (6) are independently selected from free alkyl groups, free alkoxy groups, alkenyl groups, cycloalkyl groups and aryl groups group consisting of groups.
  • the ratio of the modified polymer to the acrylate monomer is (30-80): (20-50) or (30-80): ( 0.1 ⁇ 70).
  • the structural formula of the modified polymer is formula (7) - formula (8), and the structure of formula (7) - formula (8) is as follows:
  • R 1 and R 2 in formula (7)-formula (8) are independently selected from free alkyl groups, free alkoxy groups, alkenyl groups, cycloalkyl groups and aryl groups groups in the group consisting of;
  • the adhesive matrix includes a silicone resin.
  • the siloxane resin includes polydiorganosiloxane, the terminal group and/or side group of the polydiorganosiloxane contains active hydrogen atoms, and the Each organic group in the polydiorganosiloxane is independently selected from any of free alkyl groups, free alkoxy groups, alkenyl groups, cyclohydrocarbyl groups and aryl groups .
  • the ratio of the adhesive matrix to the modified polymer is (10-80):(50-90).
  • the second aspect of the embodiment of the present application provides a preparation method of an adhesive composition.
  • the preparation method includes mixing an adhesive matrix with a modified polymer to obtain the adhesive composition, wherein the main chain of the modified polymer contains boron-oxygen coordination and/or boron-oxygen coordination bond, and the terminal group and/or side chain of the modified polymer contains at least one of hydroxyl group, acrylate group and vinyl group.
  • the modified polymer is obtained by reacting hydroxyl-terminated silicone oil with boric acid and/or diboronic acid, and the structural formula of the modified polymer is formula (1)-formula (2),
  • the structure of formula (1) - formula (2) is as follows:
  • R 1 and R 2 in formula (1)-formula (2) are independently selected from free alkyl groups, free alkoxy groups, alkenyl groups, cycloalkyl groups and aryl groups groups in the group consisting of;
  • the adhesive matrix includes at least one of silicone resin and epoxy resin.
  • the hydroxy-terminated silicone oil includes three molecular weights of the hydroxy-terminated silicone oil, and the viscosities of the three molecular weights of the hydroxy-terminated silicone oil are greater than or equal to 15,000 cps, 4,000 to 15,000 cps, and less than or equal to 4000cps.
  • the ratio of the mass parts of the hydroxyl-terminated silicone oil with a viscosity greater than or equal to 15000cps, 4000-15000cps and less than or equal to 4000cps is (30-60): (20- 50): (20-30); the total mass fraction of the boric acid and/or diboronic acid is 0.1-5.
  • the siloxane resin includes at least one polydiorganosiloxane blocked by alkoxy, acyloxy, and ketoxime groups, and the polydiorganosiloxane
  • Each organic group in the siloxane is independently selected from any one of free alkyl groups, free alkoxy groups, alkenyl groups, cyclohydrocarbyl groups and aryl groups;
  • the epoxy resin includes at least one of bisphenol A type epoxy resin and bisphenol F type epoxy resin.
  • the polydiorganosiloxane contains the above groups, which is conducive to the crosslinking reaction with the hydroxyl groups of the modified polymer.
  • the ratio of the adhesive matrix to the modified polymer is (10-80): (50-90) or (10-30): (50-90) 90).
  • the modified polymer is obtained by reacting hydroxyl-terminated silicone oil with boric acid and/or diboronic acid to obtain an intermediate, and then obtained by reacting the intermediate with isocyanate acrylate, and the modified
  • the structural formula of polymer is formula (3)-formula (4), and the structure of formula (3)-formula (4) is as follows:
  • R 1 and R 2 in formula (3)-formula (4) are independently selected from free alkyl groups, free alkoxy groups, alkenyl groups, cycloalkyl groups and aryl groups groups in the group consisting of;
  • the adhesive matrix includes acrylate monomers.
  • the ratio of the modified polymer to the acrylate monomer is (30-80):(20-50).
  • the modified polymer is obtained by reacting a hydroxyl-terminated acrylate polymer with boric acid and/or diboronic acid to form an intermediate, and then reacting the intermediate with a hydroxyacrylic acid monomer,
  • the structural formula of the modified polymer is formula (5)-formula (6), and the structure of formula (5)-formula (6) is as follows:
  • R 1 and R 2 in formula (5)-formula (6) are independently selected from free alkyl groups, free alkoxy groups, alkenyl groups, cycloalkyl groups and aryl groups Groups in the group consisting of, n is an integer greater than or equal to 1;
  • the adhesive matrix includes acrylate monomers.
  • the hydroxyl-terminated acrylate polymer is capped with boric acid and/or diboronic acid, and the hydroxyl-terminated intermediate is capped with an acrylic monomer, and then an acrylate group is introduced.
  • the reaction is easy to carry out, and the product purity High, it is easy to introduce boron-oxygen coordination and/or boron-oxygen coordination bonds into the main molecular chain of acrylate polymers, and introduce acrylate groups, which is easy to undergo cross-linking reaction with acrylate monomers.
  • the ratio of the modified polymer to the acrylate monomer in parts by mass is (30-80):(0.1-70).
  • the modified polymer is obtained by reacting a hydroxyl-terminated acrylate polymer with boric acid and/or diboronic acid to form an intermediate, which is obtained by reacting the intermediate with vinyl silicone oil, so that
  • the structural formula of described modified polymer is formula (7)-formula (8), and the structure of formula (7)-formula (8) is as follows:
  • R 1 and R 2 in formula (7)-formula (8) are independently selected from free alkyl groups, free alkoxy groups, alkenyl groups, cycloalkyl groups and aryl groups groups in the group consisting of;
  • the adhesive matrix includes a silicone resin.
  • boric acid and/or diboronic acid and hydroxyl-terminated silicone oil are used for chain extension or end-capping reaction, and the hydroxyl-terminated intermediates are capped with vinyl silicone oil, and then vinyl groups are introduced.
  • the reaction is easy to carry out, and the product High purity, easy to introduce boron-oxygen coordination and/or boron-oxygen coordination bonds into the molecular backbone of hydroxyl-terminated silicone oil polymers, and introduce vinyl groups, easy to mix with addition-curable silicone system adhesives
  • the matrix undergoes a cross-linking reaction.
  • the siloxane resin includes polydiorganosiloxane, the terminal group and/or side group of the polydiorganosiloxane contains active hydrogen atoms, the Each organic group in the polydiorganosiloxane is independently selected from any of free alkyl groups, free alkoxy groups, alkenyl groups, cyclohydrocarbyl groups and aryl groups .
  • the ratio of the adhesive matrix to the modified polymer is (10-80):(50-90).
  • the third aspect of the embodiment of the present application provides an optical adhesive film, the optical adhesive film is cured from the above-mentioned adhesive composition, and the molecular chain of the optical adhesive film contains boron-oxygen coordination and/or Even boron-oxygen coordination bonds.
  • the transmittance of the optical adhesive film is greater than or equal to 90%, the haze is less than or equal to 2.0%, and the peeling force is greater than or equal to 1.0 N/in.
  • the fourth aspect of the embodiment of the present application provides a folding screen, the folding screen includes a panel, at least one substrate layer and at least one optical adhesive film stacked on the surface of the panel, the panel and A layer of the optical adhesive film is provided between adjacent substrate layers and between two adjacent substrate layers, and the optical adhesive film is the optical adhesive film as described above.
  • the boron-oxygen coordination bond and the boron-oxygen coordination bond are introduced into the main molecular chain of the optical adhesive film. Since the boron-oxygen coordination bond or the boron-oxygen coordination bond has the aforementioned unique breakage and bonding Behavior, when subjected to impact, it can absorb energy to resist the impact of impact on the adhesive film, so that the optical adhesive film has excellent impact resistance while maintaining excellent adhesive properties and optical properties.
  • the combination of multi-layer optical adhesive film and multi-layer substrate layer can well resist external impact, improve the impact resistance of the folding screen, and reduce the failure phenomena such as black spots or broken bright spots on the panel caused by external impact.
  • a fifth aspect of the embodiment of the present application provides an electronic device, the electronic device includes the above-mentioned optical adhesive film or the above-mentioned folding screen.
  • FIG. 1 is a schematic diagram of a folding screen provided by an embodiment of the present application.
  • Fig. 2 is a schematic diagram of a falling ball experiment provided by an embodiment of the present application.
  • Fig. 3 is a comparison chart of the falling ball test results of Example 7 of the present application and Comparative Example 1.
  • optical glue OCA/LOCA
  • OCA optical glue
  • This application provides an energy-absorbing optical adhesive composition with optical performance, bonding strength and impact resistance.
  • the adhesive composition can be used as an adhesive material for bonding different substrates in folding screen electronic products, but not As a limit, each component of the adhesive composition is optimized and selected so that the adhesive composition has excellent impact resistance while maintaining excellent optical properties and bonding properties.
  • the adhesive composition includes an adhesive matrix and a modified polymer, wherein the molecular backbone of the modified polymer contains boron-oxygen coordination and/or boron-oxygen coordination bonds, and the modified polymer
  • the end groups and/or side chains of include at least one of hydroxyl groups, acrylate groups, and vinyl groups.
  • the adhesive matrix may be the base matrix of acrylate pressure-sensitive adhesives, silicone pressure-sensitive adhesives, epoxy resin pressure-sensitive adhesives.
  • the adhesive matrix may be acrylate monomers, silicone resins, epoxy resins.
  • the adhesive composition may also contain any essential and optional components required by conventional pressure-sensitive adhesives.
  • photoinitiators, antioxidants and plasticizers required for acrylate pressure-sensitive adhesives, catalysts and fillers required for silicone pressure-sensitive adhesives, cross-linking agents required for epoxy pressure-sensitive adhesives, etc.
  • At least one of a boron-oxygen coordination bond and a boron-oxygen coordination bond is introduced into the molecular main chain of the modified polymer in the present application. Due to the boron-oxygen coordination bond or the boron-oxygen coordination bond under the action of low strain rate, there is enough time for the fracture behavior to ensure that the molecular chain is flexible and bendable at low modulus; at high strain Under the effect of speed, the time scale of the molecular chain movement is much smaller than the time for the breaking of the boron-oxygen coordination bond or the boron-oxygen coordination bond, and the unbroken boron-oxygen coordination bond or the boron-oxygen coordination bond hinders the molecular The movement of the chain makes it difficult for the molecular chain to move sufficiently to untangle, and it shows the characteristics of rigidity and elasticity macroscopically.
  • the unique fracture and bonding behavior of the boron-oxygen coordination bond or above the boron-oxygen coordination bond enables the adhesive composition to have excellent impact resistance under the premise of ensuring the optical properties and bonding properties of the optical adhesive film, and can absorb The ability of external impact to resist the impact of impact on the panel.
  • active groups such as terminal hydroxyl groups, terminal acrylate groups, and terminal vinyl groups
  • Embodiment 1 (a kind of acrylate adhesive system)
  • An embodiment of the present application provides an adhesive composition
  • the adhesive composition includes an acrylate monomer and a modified polymer (PBDMSA), wherein the main chain of the modified polymer (PBDMSA) contains a boron-oxygen complex position bond and/or boron-oxygen coordination bond, and the end group is an acrylate group.
  • PBDMSA1 or PBDMSA2 the structure of the modified polymer (PBDMSA1 or PBDMSA2) is formula (3) - formula (4), formula (3) - formula (4)
  • the structure of the is as follows:
  • R 1 and R 2 in formula (3)-formula (4) are independently selected from free alkyl groups, free alkoxy groups, alkenyl groups, cycloalkyl groups and aryl groups group consisting of groups.
  • the ratio of the modified polymer (PBDMSA1 or PBDMSA2) to the acrylate monomer in parts by mass is (30-80):(20-50).
  • the adhesive composition also includes a photoinitiator, and the modified polymer (PBDMSA1 or PBDMSA2) and the acrylate monomer are polymerized and cured under the action of the photoinitiator.
  • the photoinitiator includes but is not limited to the photoinitiator required by the optical acrylate pressure-sensitive adhesive system such as model 184 and TPO.
  • the adhesive composition also includes an antioxidant and a plasticizer.
  • the antioxidants include but are not limited to antioxidants required for optical acrylate pressure-sensitive adhesive systems such as 1010 and DNP
  • the plasticizers include but are not limited to optical adhesives such as DMP and DOP. Plasticizer required for acrylate pressure sensitive adhesive systems.
  • the solvent of the adhesive composition includes but not limited to methanol, toluene, tetrahydrofuran (THF), ethyl acetate and the like.
  • the adhesive composition may also contain any essential and optional components required by conventional optical acrylate pressure-sensitive adhesive systems.
  • At least one of a boron-oxygen coordination bond and a boron-oxygen coordination bond is introduced into the main molecular chain of the optical acrylate pressure-sensitive adhesive. Because the boron-oxygen coordination bond or the boron-oxygen coordination bond has the above unique fracture and bonding behavior, the optical acrylate pressure-sensitive adhesive has excellent absorption properties under the premise of ensuring the optical properties and bonding properties of the optical adhesive film. Impact resistance, the ability to absorb the impact of external forces to resist the impact of impact on the panel. In addition, by introducing terminal acrylate groups at the end groups of the modified polymer (PBDMSA1 or PBDMSA2), it is beneficial to have a cross-linking reaction with acrylate monomers.
  • PBDMSA1 or PBDMSA2 modified polymer
  • the preparation method of above-mentioned adhesive composition specifically comprises the following steps:
  • Step S11 preparing the modified polymer (PBDMSA1 or PBDMSA2).
  • the modified polymer (PBDMS1 or PBDMS2) modified by the boron-oxygen bond is generated by the chain extension reaction of hydroxyl-terminated silicone oil and boric acid and/or diboronic acid, and the structural formula of the modified polymer (PBDMS1 or PBDMS2) is respectively formula ( 1)-formula (2), the structure of formula (1)-formula (2) is as follows:
  • R 1 and R 2 in formula (1)-formula (2) are independently selected from free alkyl groups, free alkoxy groups, alkenyl groups, cycloalkyl groups and aryl groups group consisting of groups.
  • Use boric acid and/or diboronic acid to carry out chain extension or end-capping reaction with hydroxyl-terminated silicone oil the reaction is easy to carry out, the product is of high purity, and it is easy to introduce boron-oxygen coordination and/or boron connection into the molecular main chain of hydroxyl-terminated silicone oil polymer -Oxygen coordination bonds, while introducing hydroxyl groups into the product molecular chain, which facilitates the subsequent introduction of acrylate groups.
  • the modified polymer (PBDMS1 or PBDMS2) is capped by isocyanate acrylate (such as ethyl isocyanate acrylate AOI) under the action of an organotin catalyst to obtain the modified polymer (PBDMSA1 or PBDMSA2).
  • isocyanate acrylate such as ethyl isocyanate acrylate AOI
  • R 1 in the reaction formula (I)-formula (IV) R 2 are independently selected from the group consisting of alkyl group, free alkoxy group, alkenyl group, cycloalkyl group and aryl group groups in the group.
  • the hydroxyl-terminated silicone oil is a combination of hydroxyl-terminated silicone oils with different molecular weights, including high-molecular-weight hydroxyl-terminated silicone oil with a viscosity ⁇ 15000 cps; medium-molecular-weight hydroxyl-terminated silicone oil with a viscosity of 4000 to 15000 cps; low molecular weight hydroxyl-terminated silicone oil with a viscosity of ⁇ 4000cps.
  • the mass parts of the three are 30-60, 20-50 and 20-30 respectively, and the average molecular weight and viscosity of the modified polymer (PBDMS1 or PBDMS2) can be regulated by adjusting the content of hydroxyl-terminated silicone oils with different molecular weights.
  • the mass fraction of the boric acid/diboric acid is 0.1-5.
  • the organotin catalyst includes but not limited to dibutyltin dilaurate (DBTDL).
  • DBTDL dibutyltin dilaurate
  • the solvent in the reaction process includes but not limited to methanol, toluene, THF, ethyl acetate and the like.
  • the hydroxyl-terminated silicone oil can also react with boric acid and diboronic acid at the same time to form a modified polymer ( PBDMS).
  • PBDMS modified polymer
  • Step S12 mixing the above modified polymer (PBDMSA1 or PBDMSA2) with an acrylate monomer to form the adhesive composition.
  • the adhesive composition also includes a photoinitiator, an antioxidant and a plasticizer. It can be understood that, in addition to the above components, the adhesive composition may also contain any essential and optional components required by conventional optical acrylate pressure-sensitive adhesive systems.
  • the optical adhesive film is formed by curing the above adhesive composition under light, specifically UV light curing.
  • the acrylate group on the modified polymer PBDMSA1 or PBDMSA2
  • PBDMSA1 or PBDMSA2 can undergo a cross-linking reaction with the acrylate monomer to generate a cross-linked and cured optical adhesive film.
  • the molecular chain of the optical adhesive film contains boron-oxygen Coordination and/or boron-oxygen coordination bonds.
  • the transmittance of the optical adhesive film is greater than or equal to 90%, the haze is less than or equal to 2.0%, and the peeling force is greater than or equal to 1.0N/in, which can meet the optical performance and adhesion of optical acrylate adhesives. strength requirements.
  • the adhesive strength of the optical adhesive film can also be regulated by adjusting the molecular weight of the modified polymer (PBDMSA1 or PBDMSA2) and the degree of cross-linking and curing to meet different requirements.
  • Embodiment 2 (another medium acrylate adhesive system)
  • Another embodiment of the present application provides an adhesive composition.
  • the difference between the adhesive composition and the previous embodiment is that the structure of the modified polymer (B-PAA) used in the modified acrylate adhesive system in this embodiment is the same as The previous examples used different modified polymers (PBDMSA) for the modified acrylate adhesive system.
  • the main chain of the modified polymer (B-PAA) contains a boron-oxygen coordination bond/a boron-oxygen coordination bond, and at the same time, the terminal of the modified polymer (B-PAA)
  • the radical and/or side chains contain acrylate groups.
  • R 1 and R 2 in formula (5)-formula (6) are independently selected from free alkyl groups, free alkoxy groups, alkenyl groups, cycloalkyl groups and aryl groups In the group consisting of n is an integer greater than or equal to 1.
  • At least one of a boron-oxygen coordination bond and a boron-oxygen coordination bond is introduced into the main molecular chain of the optical acrylate pressure-sensitive adhesive. Because the boron-oxygen coordination bond or the boron-oxygen coordination bond has the above unique fracture and bonding behavior, the optical acrylate pressure-sensitive adhesive has excellent absorption properties under the premise of ensuring the optical properties and bonding properties of the optical adhesive film. Impact resistance, the ability to absorb the impact of external forces to resist the impact of impact on the panel. In addition, by introducing acrylate groups into the end groups of the modified polymer (B-PAA), it is beneficial to have a crosslinking reaction with acrylate monomers.
  • B-PAA modified polymer
  • Step S21 Preparation of modified polymer (B-PAA1 or B-PAA2).
  • Boronic acid or diboronic acid is used to carry out chain extension or end-capping on the hydroxyl-terminated acrylate polymer to generate an intermediate, and then the intermediate product is capped by hydroxyethyl acrylate to generate the modified acrylate polymer.
  • Adopt diboronic acid to generate the reaction process of described modified polymer (B-PAA2) as shown in following reaction formula (VII)-formula (VIII):
  • R in formula (V)-formula (VIII) 1 is selected from the group in the group of free alkyl group, free alkoxy group, alkenyl group, cycloalkyl group and aryl group; n is an integer greater than or equal to 1.
  • the hydroxyl-terminated acrylate polymer includes, but is not limited to, hydroxyl-terminated polybutylacrylate, hydroxyl-terminated polyacrylate isooctyl, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisoprene, and the like.
  • the mass fraction of the hydroxyl-terminated acrylate polymer is 40-80.
  • the hydroxyacrylic acid monomer includes but not limited to hydroxyethyl acrylate, hydroxybutyl acrylate and the like.
  • the hydroxyacrylic acid monomer is hydroxyethyl acrylate, and the number of parts by mass is 5-40.
  • the mass fraction of the boric acid or diboronic acid is 0.1-20.
  • Step S22 Mix the above modified polymer (B-PAA1 or B-PAA2) with an acrylate monomer to form the adhesive composition.
  • the ratio of the modified polymer (B-PAA1 or B-PAA2) to the acrylate monomer in parts by mass is (30-80):(0.1-70).
  • the adhesive composition also includes a photoinitiator, an antioxidant and a plasticizer. It can be understood that, in addition to the above components, the adhesive composition may also contain any essential and optional components required by conventional optical acrylate pressure-sensitive adhesive systems.
  • the optical adhesive film is formed by curing the above adhesive composition under light, specifically UV light curing.
  • the acrylate group on the modified polymer (B-PAA1 or B-PAA2) can undergo a cross-linking reaction with the acrylate monomer to generate a cross-linked and cured optical adhesive film.
  • the molecular chain of the optical adhesive film Contains boron-oxygen coordination and/or boron-oxygen coordination bonds.
  • the transmittance of the optical adhesive film is greater than or equal to 90%, the haze is less than or equal to 2.0%, and the peeling force is greater than or equal to 1.0N/in, which can meet the optical performance and adhesion of optical acrylate adhesives. strength requirements.
  • the adhesive strength of the optical adhesive film can also be regulated by adjusting the molecular weight of the modified polymer (PBDMSA1 or PBDMSA2) and the degree of cross-linking and curing to meet different requirements.
  • Embodiment 3 (a kind of silicone adhesive system)
  • Another embodiment of the present application provides an adhesive composition, which includes the modified polymer (PBDMS1 and/or PBDMS2) in the foregoing embodiment 1 and the siloxane of the condensation-curable optical silicone pressure-sensitive adhesive system. alkane resin.
  • the siloxane resin includes polydiorganosiloxane terminated by at least one of alkoxy, acyloxy, and ketoxime groups, and each organopolysiloxane in the polydiorganosiloxane
  • the radicals are independently selected from any one of free alkyl groups, free alkoxy groups, alkenyl groups, cycloalkyl groups and aryl groups.
  • the structure of polydiorganosiloxane is shown in the following formula (9):
  • n is an integer greater than or equal to 1.
  • the ratio of the polydiorganosiloxane to the modified polymer (PBDMS1 and/or PBDMS2) in parts by mass is (10-80): (50-90).
  • the elastic modulus of the polydiorganosiloxane is less than or equal to 10 MPa
  • the light transmittance is greater than or equal to 90%
  • the haze is less than or equal to 5.0%.
  • the adhesive composition also includes a catalyst and a nano-silica filler.
  • catalysts include, but are not limited to, platinum catalysts.
  • the adhesive composition also includes nano-silica filler.
  • the adhesive composition may also contain any essential and optional components required by conventional condensation-curable silicone pressure-sensitive adhesive systems.
  • the above-mentioned adhesive composition is cured under moisture conditions to form an optical adhesive film, wherein the hydroxyl groups on the modified polymer (PBDMS1 and/or PBDMS2) can react with the alkoxy groups on the polydiorganosiloxane under room temperature moisture Condensation reaction occurs under certain conditions, and finally a cross-linked and cured optical adhesive film is generated, and the molecular chain of the optical adhesive film contains boron-oxygen coordination and/or boron-oxygen coordination bonds.
  • PBDMS1 and/or PBDMS2 modified polymer
  • n is an integer greater than or equal to 1.
  • the transmittance of the optical adhesive film is greater than or equal to 90%, the haze is less than or equal to 2.0%, and the peeling force is greater than or equal to 1.0N/in, which can meet the requirements of optical silicone pressure-sensitive adhesives on optical properties and Adhesive strength requirements.
  • the adhesive strength of the optical adhesive film can also be regulated by adjusting the molecular weight of the modified polymer (PBDMS1 or PBDMS2) and the degree of cross-linking and curing to meet different requirements.
  • This embodiment is a modified optical silicone pressure-sensitive adhesive system, by introducing at least one of a boron-oxygen coordination bond and a boron-oxygen coordination bond into the molecular backbone of the silicone pressure-sensitive adhesive. Due to the unique breaking and bonding behavior of the boron-oxygen coordination bond or even boron-oxygen coordination bond, the optical silicone pressure-sensitive adhesive has excellent cushioning under the premise of ensuring the optical properties and bonding performance of the optical film. , Energy absorption and impact resistance, able to absorb the ability of external impact to resist the impact of impact on the panel.
  • modified polymers PBDMS1 and/or PBDMS2
  • PBDMS1 and/or PBDMS2 boron-oxygen coordination bonds or boron-oxygen coordination bonds
  • condensation-curable siloxane resins to form new structural polymers to avoid boron-containing Modified polymers (PBDMS1 and/or PBDMS2) with oxygen coordination bonds or boron-oxygen coordination bonds are easy to creep and flow and have no defects in peel strength.
  • Embodiment 4 (another silicone adhesive system)
  • an adhesive composition which includes a modified polymer (PBDMSC) and a siloxane resin of an addition-type optical silicone pressure-sensitive adhesive system.
  • PBDMSC modified polymer
  • the molecular main chain of the modified polymer (PBDMSC) contains boron-oxygen coordination and/or boron-oxygen coordination bonds, and the end group and/or side chain of the modified polymer (PBDMSC) contains vinyl.
  • R 1 and R 2 in formula (7)-formula (8) are independently selected from free alkyl groups, free alkoxy groups, alkenyl groups, cycloalkyl groups and aryl groups group consisting of groups.
  • the siloxane resin includes polydiorganosiloxane, the terminal group and/or side group of the polydiorganosiloxane contains active hydrogen atoms, and the polydiorganosiloxane contains Each organic group in is independently selected from any one of free alkyl groups, free alkoxy groups, alkenyl groups, cycloalkyl groups and aryl groups.
  • the structure of polydiorganosiloxane is shown in the following formula (10):
  • the ratio of the polydiorganosiloxane to the modified polymer (PBDMSC1 and/or PBDMSC2) in parts by mass is (10-80):(50-90).
  • the elastic modulus of the polydiorganosiloxane is less than or equal to 10 MPa
  • the light transmittance is greater than or equal to 90%
  • the haze is less than or equal to 5.0%.
  • the adhesive composition also includes a catalyst and a nano-silica filler.
  • the adhesive composition may also contain any necessary and optional components required by conventional addition-curable optical silicone pressure-sensitive adhesive systems.
  • Step S41 Preparation of modified polymer (PBDMSC1 or PBDMSC2).
  • the modified polymer (PBDMSC1 or PBDMSC2) is obtained by capping the modified polymer (PBDMS1 or PBDMS2) in the foregoing Example 1 through vinyl silicone oil, and the structure of the vinyl silicone oil is shown in the following formula (11):
  • Step S42 mixing the above modified polymer (PBDMSC1 and/or PBDMSC2) with the siloxane resin represented by formula (10) and other components to form the adhesive composition.
  • the above-mentioned adhesive composition is cured under heating conditions to form an optical adhesive film, wherein the vinyl group on the modified polymer (PBDMSC1 or PBDMSC2) can react with the active hydrogen atoms on the polydiorganosiloxane under heating and conditions Addition polymerization reaction occurs under the condition, and finally a cross-linked and cured optical adhesive film is generated, and the molecular chain of the optical adhesive film contains boron-oxygen coordination and/or boron-oxygen coordination bonds.
  • PBDMSC1 or PBDMSC2 the vinyl group on the modified polymer
  • Addition polymerization reaction occurs under the condition, and finally a cross-linked and cured optical adhesive film is generated, and the molecular chain of the optical adhesive film contains boron-oxygen coordination and/or boron-oxygen coordination bonds.
  • the transmittance of the optical adhesive film is greater than or equal to 90%, the haze is less than or equal to 2.0%, and the peeling force is greater than or equal to 1.0N/in, which can meet the requirements of optical silicone pressure-sensitive adhesives on optical properties and Adhesive strength requirements.
  • the adhesive strength of the optical adhesive film can also be regulated by adjusting the molecular weight of the modified polymer (PBDMS1 and/or PBDMS2) and the degree of cross-linking and curing, so as to meet different requirements.
  • This embodiment is another modified optical silicone pressure-sensitive adhesive system, by introducing at least one of the boron-oxygen coordination bond and the boron-oxygen coordination bond into the molecular backbone of the silicone pressure-sensitive adhesive . Because the boron-oxygen coordination bond or the boron-oxygen coordination bond has the above unique fracture and bonding behavior, the optical silicone pressure-sensitive adhesive has excellent cushioning under the premise of ensuring the optical properties and bonding performance of the optical film. , Energy absorption and impact resistance, able to absorb the ability of external impact to resist the impact of impact on the panel.
  • the modified polymer (PBDMSC1 and/or PBDMSC2) can be cured and molded by adding a curable siloxane resin to form a new structure polymer to avoid the easy creep of the boron-containing modified polymer (PBDMSC1 and/or PBDMSC2) Runny with no peel strength imperfections.
  • Embodiment 5 epoxy resin adhesive system
  • Yet another embodiment of the present application provides an adhesive composition, which includes the modified polymer (PBDMS1 and/or PBDMS2) in the foregoing embodiment 1 and an epoxy resin.
  • the epoxy resin may be any epoxy resin, specifically at least one of bisphenol A epoxy resin and bisphenol F epoxy resin.
  • the adhesive composition further includes a crosslinking agent
  • the tertiary amine crosslinking agent includes but not limited to acid anhydrides, amines, dicyandiamide and the like.
  • the ratio of the epoxy resin to the modified polymer in parts by mass is (10-30): (30-60).
  • the adhesive composition may also contain any essential and optional components required by conventional optical epoxy pressure-sensitive adhesive systems.
  • This embodiment also provides an optical adhesive film, which is formed by curing the above-mentioned adhesive composition under heating conditions, and the hydroxyl groups on the modified polymer (PBDMS1 or PBDMS2) can be combined with the epoxy groups of the epoxy resin. The group undergoes a polymerization reaction under heating and conditions, and finally generates a cross-linked and cured optical adhesive film.
  • the molecular chain of the optical adhesive film contains boron-oxygen coordination and/or boron-oxygen coordination bonds.
  • R in the reaction formula (XII)-reaction formula (XIII) is the residue of bisphenol A or bisphenol F; each n is an integer greater than or equal to 1, and the modified polymerization described in this embodiment Both R1 and R2 are methyl in the compound (PBDMS1 or PBDMS2).
  • the epoxy resin adhesive product obtained by the reaction formula (XII)-reaction formula (XIII) is a linear structure and is liquid, and other fillers (such as nano silicon dioxide, plasticizer, etc.) can also be added in the anhydride class Under the action of curing agents such as amines or amines, it is further cross-linked and cured to form a cross-linked network structure.
  • the transmittance of the optical adhesive film is greater than or equal to 90%, the haze is less than or equal to 2.0%, and the peeling force is greater than or equal to 1.0N/in, which can meet the optical properties of optical epoxy pressure-sensitive adhesives. and bond strength requirements.
  • the adhesive strength of the optical adhesive film can also be regulated by adjusting the molecular weight of the modified polymer (PBDMS1 and/or PBDMS2) and the degree of cross-linking and curing, so as to meet different requirements.
  • This embodiment is a modified optical epoxy resin pressure-sensitive adhesive system, by introducing at least one of a boron-oxygen coordination bond and a boron-oxygen coordination bond into the molecular backbone of the epoxy resin pressure-sensitive adhesive. Because the boron-oxygen coordination bond or the boron-oxygen coordination bond has the above unique fracture and bonding behavior, the optical epoxy resin pressure-sensitive adhesive has excellent performance under the premise of ensuring the optical properties and bonding performance of the optical adhesive film. Cushioning, energy absorption and impact resistance, the ability to absorb the impact of external forces to resist the impact of impact on the panel.
  • the present application also provides a folding screen 100, which includes a panel 10, a multi-layer substrate layer 20 and an optical adhesive film 30 stacked on the front of the panel 10, wherein the panel 10 and the A layer of optical adhesive film 30 is provided between adjacent substrate layers 20 and between two adjacent substrate layers 20 .
  • the optical adhesive film 30 is formed by curing any one of the aforementioned adhesive compositions. According to the aforementioned different adhesive compositions, different curing methods are adopted.
  • the folding screen 100 can be prepared through the following two processes.
  • the first process is: prepare any one of the aforementioned adhesive compositions, and vacuum defoam the adhesive composition; apply the defoamed adhesive composition on the substrate layer 20, and perform curing to obtain the optical adhesive film 30 Cover the release film on the surface of the optical adhesive film 30, thereby preparing a single-sided optical tape, and die-cut the single-sided optical tape; remove the die-cut single-sided optical tape and attach it to the panel 10 after removing the release film
  • On the front side if multiple substrate layers 20 need to be bonded, single-sided optical tapes can be bonded sequentially, and defoaming is performed again to obtain the folding screen 100 .
  • both surfaces of the substrate layer 20 located in the middle can be coated with an adhesive composition to prepare a double-sided optical adhesive tape.
  • the optical adhesive film 30 with different numbers of layers and different thicknesses can be designed according to the requirements of the impact resistance performance of the actual product.
  • the folding screen 100 may also include a conventional optical adhesive film.
  • the second process is: prepare any of the aforementioned adhesive compositions, and carry out vacuum defoaming of the adhesive composition; spot-coat or spray the defoamed adhesive composition on the front of the panel 10 to form an uncured adhesive film (Fig. not shown), then attach the substrate layer 20 to the surface of the uncured adhesive film, vacuum defoaming is performed again, and after defoaming, solidify to obtain the optical adhesive film 30. If it is necessary to attach multiple substrate layers 20, you can The above-mentioned method is repeated to sequentially form a multi-layer optical adhesive film 30 , so as to obtain the folding screen 100 .
  • This process is a lamination first and then curing process, which can be applied to the situation of local bonding, without the need for large-scale glue distribution, and the operation is more flexible.
  • the material of the substrate layer 20 includes but not limited to PI or PET.
  • the boron-oxygen coordination bond and the boron-oxygen coordination bond are introduced into the main molecular chain of the optical adhesive film 30. Since the boron-oxygen coordination bond or the boron-oxygen coordination bond has the aforementioned unique breaking and bonding behavior, in When subjected to an impact, it can absorb energy to resist the impact of the impact on the adhesive film, so that the optical adhesive film 30 has excellent impact resistance under the premise of maintaining excellent adhesive performance and optical performance.
  • the multi-layer optical adhesive film 30 combined with the multi-layer substrate layer 20 can well resist external impact, improve the impact resistance of the folding screen, and reduce the failure phenomena such as black spots or broken bright spots on the panel 10 caused by external impact.
  • PBDMSA1 modified silicone oil polymer
  • PBDMSA1 or PBDMSA2 The raw material formula of synthetic modified silicone oil polymer (PBDMSA1 or PBDMSA2) is shown in Table 2.
  • PBDMSC1 modified silicone oil polymer
  • PBDMSC1 or PBDMSC2 The raw material formulation of synthetic modified silicone oil polymer (PBDMSC1 or PBDMSC2) is shown in Table 4.
  • the raw material formulation of the synthetic adhesive composition is shown in Table 5.
  • B-PAA1 and/or B-PAA2 Synthesis Example 3 30-80 Acrylate monomer Butyl acrylate, lauryl acrylate, etc. 0-70 Photoinitiator 184. TPO, etc. 0-5 antioxidant Antioxidant 1010, Antioxidant DNP, etc. 0-5 plasticizer DMP, DOP, etc. 0-50
  • Table 7 shows the raw material formula for preparing the adhesive composition of the silicone system.
  • Table 8 shows the raw material formula for preparing another silicone-based adhesive composition.
  • the linear epoxy resin adhesive prepared in (2) was mixed according to the formula shown in Table 10 below and further cured to obtain a cross-network adhesive.
  • a folding screen :
  • the two layers of optical adhesive film are respectively located between the panel and the PI base material and between the two layers of PI base material.
  • the thickness of the film is 50 ⁇ m
  • the optical adhesive film is the optical adhesive film of the boron-oxygen coordination bond modified silicone adhesive system prepared in Example 3 of the present application.
  • the film thickness is 50 ⁇ m
  • the optical adhesive film is the optical adhesive film of the existing silicone adhesive system.
  • Example 3 of the present application Use the boron-oxygen coordination bond modified organic silica gel adhesive prepared in Example 3 of the present application to prepare a folding screen, and conduct a steel ball impact test.
  • the steel ball weighs 32g and has a diameter of 20mm.
  • the steel ball test is shown in Figure 2. Two tests were performed.
  • the failure height of the foldable screen with broken bright spots under the impact of steel balls, the test results are shown in Figure 3, the minimum failure height of the foldable screen of Comparative Example 1 with broken bright spots is 73 cm, and the foldable screen of Example 6 of the present application has no broken bright spots.
  • the minimum failure height of the bright spot is 91cm, which is significantly improved compared with Comparative Example 1.
  • this application introduces the boron-oxygen coordination bond and the boron-oxygen coordination bond into the main molecular chain of the optical adhesive film, because the boron-oxygen coordination bond or the boron-oxygen coordination bond has the aforementioned unique breakage and bonding Behavior, when subjected to impact, it can absorb energy to resist the impact of impact on the adhesive film, so that the optical adhesive film has excellent impact resistance while maintaining excellent adhesive properties and optical properties.
  • the combination of multi-layer optical adhesive film and multi-layer substrate layer can well resist external impact, improve the impact resistance of the folding screen, and reduce the failure phenomena such as black spots or broken bright spots on the panel caused by external impact.

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Abstract

本申请提供一种胶粘剂组合物，该胶粘剂组合物包括胶粘剂基体以及改性聚合物，其中，所述改性聚合物的主链中包含硼-氧配位和/或连硼-氧配位键，所述改性聚合物的端基和/或侧链包含羟基、丙烯酸酯基、乙烯基中的至少一种。本申请还提供了一种该树脂组合物的制备方法、光学胶膜、应用该光学胶膜的折叠屏、及应用该光学胶膜或折叠屏的电子设备。本申请在改性聚合物的分子主链中引入硼-氧配位键和/或连硼-氧配位键，使胶粘剂组合物在保证粘接强度的前提下具有优异的吸能抗冲击性能，进而提高折叠屏的抗冲击性能，降低外力冲击使面板出现黑斑或者碎亮点等失效现象。

Description

胶粘剂组合物及其制备方法、光学胶膜及其应用
相关申请的交叉引用
本申请要求在2021年12月20日提交中国专利局、申请号为202111566821.8、申请名称为“胶粘剂组合物及其制备方法、光学胶膜及其应用”的中国专利的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及一种胶粘剂组合物、该胶粘剂组合物的制备方法、由该胶粘剂组合物制备的光学胶膜、含有该光学胶膜的折叠屏、以及含有该光学胶膜或该折叠屏的电子设备。
背景技术
折叠屏电子设备由于其屏幕可折叠，为用户在阅读，游戏和办公等领域带来了全新的视觉体验和便利，越来越受到人们的青睐。
目前，折叠屏的结构主要包括面板以及位于面板正面的盖板，其中盖板的基材为具有优良的可弯折性能的有机膜材，例如聚酰亚胺膜(PI)、聚对苯二甲酸乙二醇酯膜(PET)等。其中盖板中的相邻两层基材之间以及盖板与面板之间均通过光学胶(Optical Clear Adhesive，OCA)或液态光学胶(Liquid Optical Clear Adhesive，LOCA)粘接在一起。
然而，现有的OCA/LOCA体系大多为丙烯酸酯类聚合物体系或者硅胶类聚合物体系，弹性模量过低，约为10Kpa～500Kpa，屏幕受到冲击之后，由于有机膜材具有柔性，不能很好地抵抗外力冲击，很容易发生形变，使较强外力作用于OCA/LOCA膜层，但现有的OCA/LOCA的抗冲击性能较差，冲击能量无法被吸收或者耗散，进而传递到面板导致面板上出现黑斑或者碎亮点等失效现象。
发明内容
本申请实施例第一方面提供了一种胶粘剂组合物，所述胶粘剂组合物包括胶粘剂基体以及改性聚合物，其中，所述改性聚合物的主链中包含硼-氧配位和/或连硼-氧配位键，所述改性聚合物的端基和/或侧链包含羟基、丙烯酸酯基、乙烯基中的至少一种。
可以看出，本申请改性聚合物的分子主链中引入了硼-氧配位键和连硼-氧配位键中的至少一种。由于硼-氧配位键或连硼-氧配位键在低应变速率作用下，有足够的时间发生断裂行为，从而保证分子链在低模量下具有柔性和可弯折性；在高应变速率作用下，分子链运动的时间尺度远小于硼-氧配位键或连硼-氧配位键断裂的时间，未断裂的硼-氧配位键或连硼-氧配位键阻碍了分子链的运动，使分子链很难充分运动以发生解缠，宏观上表现出刚性与弹性的特点。硼-氧配位键或连硼-氧配位键以上独特的断裂与键合行为，使胶粘剂组合物在保证粘接强度的前提下具有优异的吸能抗冲击性能，能够吸收外力冲击产生的能力以抵抗冲击作用对面板的影响。另外，通过在改性聚合物的端基引入端羟基、端丙烯酸酯基、端乙烯基等活 性基团，有利于与胶粘剂基体或丙烯酸酯单体发生交联反应。
结合第一方面，在一些实施例中，所述改性聚合物的结构式为式(1)-式(2)，式(1)-式(2)的结构如下所示：
Figure PCTCN2022138515-appb-000001
其中，式(1)-式(2)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团；
所述胶粘剂基体包括硅氧烷树脂和环氧树脂中的至少一种。
结合第一方面，在一些实施例中，所述硅氧烷树脂包括烷氧基、酰氧基、酮肟基中的至少一种封端的聚二有机基硅氧烷，所述聚二有机基硅氧烷中的每个有机基独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烃基基团和芳基基团中的任一种；
所述环氧树脂包括双酚A型环氧树脂和双酚F型环氧树脂中的至少一种。
结合第一方面，在一些实施例中，所述胶粘剂基体与所述改性聚合物的质量份数之比为(10～80)：(50～90)或(10～30)：(50～90)。
结合第一方面，在一些实施例中，所述改性聚合物的结构式为式(3)-式(6)，式(3)-式(6)的结构如下所示：
Figure PCTCN2022138515-appb-000002
其中，式(3)-式(6)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团。
结合第一方面，在一些实施例中，所述改性聚合物与所述丙烯酸酯单体的质量份数之比为(30～80)：(20～50)或(30～80)：(0.1～70)。
结合第一方面，在一些实施例中，所述改性聚合物的结构式为式(7)-式(8)，式(7)-式(8)的结构如下所示：
Figure PCTCN2022138515-appb-000003
Figure PCTCN2022138515-appb-000004
其中，式(7)-式(8)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团；
所述胶粘剂基体包括硅氧烷树脂。
结合第一方面，在一些实施例中，所述硅氧烷树脂包括聚二有机基硅氧烷，所述聚二有机基硅氧烷的端基和/或侧基含有活泼氢原子，所述聚二有机基硅氧烷中的每个有机基独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烃基基团和芳基基团中的任一种。
结合第一方面，在一些实施例中，所述胶粘剂基体与所述改性聚合物的质量份数之比为(10～80)：(50～90)。
本申请实施例第二方面提供了一种胶粘剂组合物的制备方法，所述制备方法包括将胶粘剂基体与改性聚合物混合得到所述胶粘剂组合物，其中，所述改性聚合物的主链中包含硼-氧配位和/或连硼-氧配位键，所述改性聚合物的端基和/或侧链包含羟基、丙烯酸酯基、乙烯基中的至少一种。
结合第二方面，在一些实施例中，所述改性聚合物通过端羟基硅油与硼酸和/或二硼酸反应得到，所述改性聚合物的结构式为式(1)-式(2)，式(1)-式(2)的结构如下所示：
Figure PCTCN2022138515-appb-000005
其中，式(1)-式(2)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团；
所述胶粘剂基体包括硅氧烷树脂和环氧树脂中的至少一种。
可以看出，采用硼酸和/或二硼酸与端羟基硅油进行扩链或封端反应，反应易于进行，产物纯度高，容易在端羟基硅油聚合物的分子主链中引入硼-氧配位和/或连硼-氧配位键；另外，由于形成的改性聚合物的分子链中含有羟基，易与胶粘剂基体发生交联反应。
结合第二方面，在一些实施例中，所述端羟基硅油包括三种分子量的端羟基硅油，三种分子量的所述端羟基硅油的粘度分别为大于或等于15000cps、4000～15000cps以及小于或等于4000cps。
结合第二方面，在一些实施例中，粘度分别为大于或等于15000cps、4000～15000cps以及小于或等于4000cps的所述端羟基硅油以及的质量份数之比为(30～60)：(20～50)：(20～30)；所述硼酸和/或二硼酸的总的质量份数为0.1～5。
可以看出，按不同的比例添加具有不同分子量的端羟基硅油，可以调整生成的改性聚合物的粘度，以调控最终胶粘剂体系的粘度，满足不同的粘度需求。
结合第二方面，在一些实施例中，所述硅氧烷树脂包括烷氧基、酰氧基、酮肟基中的至 少一种封端的聚二有机基硅氧烷，所述聚二有机基硅氧烷中的每个有机基独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烃基基团和芳基基团中的任一种；
所述环氧树脂包括双酚A型环氧树脂和双酚F型环氧树脂中的至少一种。
可以看出，聚二有机基硅氧烷中含有上述基团，有利于与改性聚合物的羟基发生交联反应。
结合第二方面，在一些实施例中，所述胶粘剂基体与所述改性聚合物的质量份数之比为(10～80)：(50～90)或(10～30)：(50～90)。
结合第二方面，在一些实施例中，所述改性聚合物通过端羟基硅油与硼酸和/或二硼酸反应得到中间体，再通过所述中间体与异氰酸酯丙烯酸酯反应得到，所述改性聚合物的结构式为式(3)-式(4)，式(3)-式(4)的结构如下所示：
Figure PCTCN2022138515-appb-000006
其中，式(3)-式(4)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团；
所述胶粘剂基体包括丙烯酸酯单体。
可以看出，采用硼酸和/或二硼酸与端羟基硅油进行扩链或封端反应，并对中间体的端羟基进行封端进而引入丙烯酸酯基团，反应易于进行，产物纯度高，容易在端羟基硅油聚合物的分子主链中引入硼-氧配位和/或连硼-氧配位键，并引入丙烯酸酯基团，易与丙烯酸酯单体发生交联反应。
结合第二方面，在一些实施例中，所述改性聚合物与所述丙烯酸酯单体的质量份数之比为(30～80)：(20～50)。
结合第二方面，在一些实施例中，所述改性聚合物通过端羟基丙烯酸酯聚合物与硼酸和/或二硼酸反应生成中间体，再通过所述中间体与羟基丙烯酸单体反应得到，所述改性聚合物的结构式为式(5)-式(6)，式(5)-式(6)的结构如下所示：
Figure PCTCN2022138515-appb-000007
其中，式(5)-式(6)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团，n为大于或等于1的整数；
所述胶粘剂基体包括丙烯酸酯单体。
可以看出，采用硼酸和/或二硼酸对端羟基丙烯酸酯聚合物进行封端，并对中间体的端羟基采用丙烯酸单体进行封端，进而引入丙烯酸酯基团，反应易于进行，产物纯度高，容易在丙烯酸酯聚合物的分子主链中引入硼-氧配位和/或连硼-氧配位键，并引入丙烯酸酯基团，易与丙烯酸酯单体发生交联反应。
结合第二方面，在一些实施例中，所述改性聚合物与所述丙烯酸酯单体的质量份数之比为(30～80)：(0.1～70)。
结合第二方面，在一些实施例中，所述改性聚合物通过端羟基丙烯酸酯聚合物与硼酸和/或二硼酸反应生成中间体，在通过所述中间体与乙烯基硅油反应得到，所述改性聚合物的结构式为式(7)-式(8)，式(7)-式(8)的结构如下所示：
Figure PCTCN2022138515-appb-000008
其中，式(7)-式(8)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团；
所述胶粘剂基体包括硅氧烷树脂。
可以看出，采用硼酸和/或二硼酸与端羟基硅油进行扩链或封端反应，并对中间体的端羟基采用乙烯基硅油进行封端，进而引入乙烯基基团，反应易于进行，产物纯度高，容易在端羟基硅油聚合物的分子主链中引入硼-氧配位和/或连硼-氧配位键，并引入乙烯基基团，易与加成固化型有机硅体系的胶粘剂基体发生交联反应。
结合第二方面，在一些实施例中，所述硅氧烷树脂包括聚二有机基硅氧烷，所述聚二有机基硅氧烷的端基和/或侧基含有活泼氢原子，所述聚二有机基硅氧烷中的每个有机基独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烃基基团和芳基基团中的任一种。
结合第二方面，在一些实施例中，所述胶粘剂基体与所述改性聚合物的质量份数之比为(10～80)：(50～90)。
本申请实施例第三方面提供了一种光学胶膜，所述光学胶膜由如上所述的胶粘剂组合物固化而成，所述光学胶膜的分子链中包含硼-氧配位和/或连硼-氧配位键。
结合第三方面，在一些实施例中，所述光学胶膜的透过率大于或等于90％，雾度小于或等于2.0％，剥离力大于或等于1.0N/in。
本申请实施例第四方面提供了一种折叠屏，所述折叠屏包括面板以及叠设于所述面板的表面的至少一层基材层和至少一层光学胶膜，所述面板和与之相邻的所述基材层之间、以及相邻两所述基材层之间均设有一层所述光学胶膜，所述光学胶膜为如上所述的光学胶膜。
可以看出，光学胶膜的分子主链中引入了硼氧配位键和连硼氧配位键，由于硼-氧配位键或连硼-氧配位键具有前述独特的断裂与键合行为，在受到冲击作用时，能够吸收能量以抵抗冲击作用对胶膜的影响，使光学胶膜在维持优良的粘接性能和光学性能的前提下具有优异的抗冲击性能。多层光学胶膜结合多层基材层可以很好地抵抗外力冲击，提高折叠屏的抗冲击性能，降低外力冲击使面板出现黑斑或者碎亮点等失效现象。
本申请实施例第五方面提供了一种电子设备，该电子设备包括如上所述的光学胶膜或如上所述的折叠屏。
附图说明
图1是本申请一实施例提供的折叠屏的示意图。
图2是本申请一实施例提供的落球实验的示意图。
图3是本申请实施例七与对比例一的落球实验结果对照图。
主要元件符号说明
折叠屏          100
面板            10
基材层          20
光学胶膜        30
高度            h
具体实施方式
下面结合本申请实施例中的附图对本申请实施例进行描述。本申请中涉及的数据范围如无特别说明均应包括端值。
常用的光学胶(OCA/LOCA)抗冲击性能差，在将光学胶应用到折叠屏电子产品后，折叠屏在外力冲击作用下屏幕容易出现黑斑或者碎亮点等失效现象。
本申请提供一种兼具光学性能、粘接强度和抗冲击性能的吸能型光学胶粘剂组合物，该胶粘剂组合物可作为折叠屏电子产品中粘接不同基材的粘接材料使用，但不以此为限，合成该胶粘剂组合物的各个组分经过优化选型，使所述胶粘剂组合物在维持优良的光学性能和粘接性能的前提下具有优异的抗冲击性能。
所述胶粘剂组合物包括胶粘剂基体以及改性聚合物，其中，所述改性聚合物的分子主链中包含硼-氧配位和/或连硼-氧配位键，所述改性聚合物的端基和/或侧链包括羟基、丙烯酸酯基、乙烯基中的至少一种。
所述胶粘剂基体可以是丙烯酸酯压敏胶粘剂、有机硅压敏胶粘剂、环氧树脂压敏胶粘剂的基础基体。例如，所述胶粘剂基体可以是丙烯酸酯单体、硅氧烷树脂、环氧树脂。
可以理解的，所述胶粘剂组合物除了以上组分外，其还可以包含常规压敏胶粘剂所需的任何必要和非必要组分。例如，丙烯酸酯压敏胶粘剂所需要的光引发剂、抗氧剂和增塑剂等，有机硅压敏胶粘剂所需要的催化剂和填料等，环氧树脂压敏胶粘剂所需要交联剂等。
本申请改性聚合物的分子主链中引入了硼-氧配位键和连硼-氧配位键中的至少一种。由于硼-氧配位键或连硼-氧配位键在低应变速率作用下，有足够的时间发生断裂行为，从而保证分子链在低模量下具有柔性和可弯折性；在高应变速率作用下，分子链运动的时间尺度远小于硼-氧配位键或连硼-氧配位键断裂的时间，未断裂的硼-氧配位键或连硼-氧配位键阻碍了分子链的运动，使分子链很难充分运动以发生解缠，宏观上表现出刚性与弹性的特点。硼-氧配位键或连硼-氧配位键以上独特的断裂与键合行为，使胶粘剂组合物在保证光学胶膜光学性能和粘接性能的前提下具有优异的抗冲击性能，能够吸收外力冲击产生的能力以抵抗冲击作用对面板的影响。另外，通过在改性聚合物的端基引入端羟基、端丙烯酸酯基、端乙烯基等活性基团，有利于与丙烯酸酯单体、硅氧烷树脂和环氧树脂之间发生交联反应。
以下实施例中根据不同的光学压敏胶粘剂体系，采用不同的改性聚合物对其进行改性，在保证光学压敏胶粘剂的光学性能和粘接性能的前提下，赋予相应的光学压敏胶粘剂以优异 的吸能抗冲击性能。
实施例1(一种丙烯酸酯胶粘剂体系)
本申请一实施例提供了一种胶粘剂组合物，该胶粘剂组合物包括丙烯酸酯单体和改性聚合物(PBDMSA)，其中，该改性聚合物(PBDMSA)的主链中含有硼-氧配位键和/或连硼-氧配位键，端基为丙烯酸酯基。根据引入的硼-氧配位键还是连硼-氧配位键，改性聚合物(PBDMSA1或PBDMSA2)的结构分别为式(3)-式(4)，式(3)-式(4)的结构如下所示：
Figure PCTCN2022138515-appb-000009
其中，式(3)-式(4)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团。
进一步地，所述改性聚合物(PBDMSA1或PBDMSA2)与所述丙烯酸酯单体的质量份数之比为(30～80)：(20～50)。
进一步地，所述胶粘剂组合物还包括光引发剂，所述改性聚合物(PBDMSA1或PBDMSA2)和丙烯酸酯单体在光引发剂的作用下发生聚合反应并固化。本实施例中，所述光引发剂包括但不限于型号为184和TPO等光学丙烯酸酯压敏胶粘剂体系所需的光引发剂。
进一步地，所述胶粘剂组合物还包括抗氧剂和增塑剂。本实施例中，所述抗氧剂包括但不限于型号为1010和DNP等光学丙烯酸酯压敏胶粘剂体系所需的抗氧剂，所述增塑剂包括但不限于型号为DMP、DOP等光学丙烯酸酯压敏胶粘剂体系所需的增塑剂。
进一步地，所述胶粘剂组合物的溶剂包括但不限于甲醇、甲苯、四氢呋喃(THF)、乙酸乙酯等。
可以理解的，所述胶粘剂组合物中除了以上组分外，还可以包含常规光学丙烯酸酯压敏胶粘剂体系所需的任何必要和非必要组分。
本实施例在光学丙烯酸酯压敏胶粘剂的分子主链中引入了硼-氧配位键和连硼-氧配位键中的至少一种。由于硼-氧配位键或连硼-氧配位键具有以上独特的断裂与键合行为，使光学丙烯酸酯压敏胶粘剂在保证光学胶膜光学性能和粘接性能的前提下具有优异的吸能抗冲击性能，能够吸收外力冲击产生的能力以抵抗冲击作用对面板的影响。另外，通过在改性聚合物(PBDMSA1或PBDMSA2)的端基引入端丙烯酸酯基团，有利于与丙烯酸酯单体之间发生交联反应。
上述胶粘剂组合物的制备方法具体包括以下步骤：
步骤S11：制备所述改性聚合物(PBDMSA1或PBDMSA2)。
首先通过端羟基硅油与硼酸和/或二硼酸的扩链反应生成硼氧键改性的改性聚合物(PBDMS1或PBDMS2)，所述改性聚合物(PBDMS1或PBDMS2)的结构式分别为式(1)-式(2)，式(1)-式(2)的结构如下所示：
Figure PCTCN2022138515-appb-000010
其中，式(1)-式(2)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团。采用硼酸和/或二硼酸与端羟基硅油进行扩链或封端反应，反应易于进行，产物纯度高，容易在端羟基硅油聚合物的分子主链中引入硼-氧配位和/或连硼-氧配位键，同时在产物分子链中引入羟基，便于后续引入丙烯酸酯基团。
再将改性聚合物(PBDMS1或PBDMS2)在有机锡催化剂的作用下通过异氰酸酯丙烯酸酯(例如异氰酸酯丙烯酸乙酯AOI)封端，从而获得所述改性聚合物(PBDMSA1或PBDMSA2)。
采用硼酸合成胶粘剂基体(PBDMSA1)的反应过程如下反应式(I)-反应式(II)所示：
Figure PCTCN2022138515-appb-000011
采用二硼酸合成改性聚合物(PBDMSA2)的反应过程如下反应式(III)-反应式(IV)所示：
Figure PCTCN2022138515-appb-000012
反应式(I)-式(IV)中的R 1，R 2分别独立地选自烷基基团、自由烷氧基基团、链烯基 基团、环烷基基团和芳基组成的组中的基团。
进一步地，所述端羟基硅油为不同分子量的端羟基硅油的组合，其中包括高分子量端羟基硅油，粘度≥15000cps；中分子量端羟基硅油，粘度为4000～15000cps；低分子量端羟基硅油，粘度为≤4000cps。三者的质量份数分别为30～60、20～50和20～30，可以通过调节不同分子量端羟基硅油的含量进而调控改性聚合物(PBDMS1或PBDMS2)的平均分子量和粘度。所述硼酸/二硼酸的质量份数为0.1～5。
进一步地，所述有机锡催化剂包括但不限于二月桂酸二丁基锡(DBTDL)。
进一步地，反应过程中的溶剂包括但不限于甲醇、甲苯、THF、乙酸乙酯等。
可以理解的，在其他实施例中，端羟基硅油还可以同时与硼酸和二硼酸进行反应，形成分子链中同时含有硼-氧配位键和连硼-氧配位键的改性聚合物(PBDMS)。
步骤S12：将以上改性聚合物(PBDMSA1或PBDMSA2)与丙烯酸酯单体混合，以形成所述胶粘剂组合物。
进一步地，该胶粘剂组合物中还包括光引发剂、抗氧剂和增塑剂。可以理解的，所述胶粘剂组合物中除了以上组分外，还可以包含常规光学丙烯酸酯压敏胶粘剂体系所需的任何必要和非必要组分。
上述胶粘剂组合物用作一种光学胶膜时，该光学胶膜通过以上胶粘剂组合物在光照下固化而成，具体为UV光固化。其中，改性聚合物(PBDMSA1或PBDMSA2)上的丙烯酸酯基团能与丙烯酸酯单体发生交联反应，进而生成交联固化的光学胶膜，该光学胶膜的分子链中含有硼-氧配位和/或连硼-氧配位键。
本实施例中，所述光学胶膜的透过率大于或等于90％，雾度小于或等于2.0％，剥离力大于或等于1.0N/in，能够满足光学丙烯酸酯胶对光学性能和粘接强度的要求。另外，还可以通过调整改性聚合物(PBDMSA1或PBDMSA2)的分子量以及交联固化程度调控光学胶膜的粘接强度，以满足不同的需求。
实施例2(另一中丙烯酸酯胶粘剂体系)
本申请另一实施例提供了一种胶粘剂组合物，该胶粘剂组合物与前述实施例的区别在于：本实施例用于改性丙烯酸酯胶粘剂体系的改性聚合物(B-PAA)的结构与前述实施例用于改性丙烯酸酯胶粘剂体系的改性聚合物(PBDMSA)不同。本实施例中，所述改性聚合物(B-PAA)的主链含有硼-氧配位键/连硼-氧配位键，同时，所述改性聚合物(B-PAA)的端基和/或侧链含有丙烯酸酯基团。
进一步地，所述改性聚合物(B-PAA1或B-PAA2)的结构为式(5)-式(6)，式(5)-式(6)的结构如下所示：
Figure PCTCN2022138515-appb-000013
其中，式(5)-式(6)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团，n为大于或等于1的整数。
本实施例在光学丙烯酸酯压敏胶粘剂的分子主链中引入了硼-氧配位键和连硼-氧配位键中的至少一种。由于硼-氧配位键或连硼-氧配位键具有以上独特的断裂与键合行为，使光学丙烯酸酯压敏胶粘剂在保证光学胶膜光学性能和粘接性能的前提下具有优异的吸能抗冲击性能，能够吸收外力冲击产生的能力以抵抗冲击作用对面板的影响。另外，通过在改性聚合物(B-PAA)的端基引入丙烯酸酯基团，有利于与丙烯酸酯单体之间发生交联反应。
本实施例中胶粘剂组合物的制备方法具体包括以下步骤：
步骤S21：改性聚合物(B-PAA1或B-PAA2)的制备。
采用硼酸或二硼酸对端羟基丙烯酸酯聚合物进行扩链或封端生成中间体，再将中间产物通过丙烯酸羟乙酯进行封端生成所述改性丙烯酸酯聚合物。
采用硼酸生成所述改性聚合物(B-PAA1)的反应过程如下反应式(V)-式(VI)所示：
Figure PCTCN2022138515-appb-000014
采用二硼酸生成所述改性聚合物(B-PAA2)的反应过程如下反应式(VII)-式(VIII)所示：
Figure PCTCN2022138515-appb-000015
式(V)-式(VIII)中的R 1选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团；n为大于或等于1的整数。
进一步地，所述端羟基丙烯酸酯聚合物包括但不限于端羟基聚丙烯酸丁酯、端羟基聚丙烯酸异辛酯、端羟基聚丁二烯、端羟基聚异戊二烯等。本实施中，所述端羟基丙烯酸酯聚合物的质量份数为40-80。
进一步地，所述羟基丙烯酸单体包括但不限于丙烯酸羟乙酯、丙烯酸羟丁酯等。本实施例中，所述羟基丙烯酸单体为丙烯酸羟乙酯，质量份数为5-40。
进一步地，所述硼酸或二硼酸的质量份数为0.1～20。
步骤S22：将以上改性聚合物(B-PAA1或B-PAA2)与丙烯酸酯单体混合，以形成所述 胶粘剂组合物。
进一步地，所述改性聚合物(B-PAA1或B-PAA2)与丙烯酸酯单体的质量份数之比为(30～80)：(0.1～70)。
进一步地，该胶粘剂组合物中还包括光引发剂、抗氧剂和增塑剂。可以理解的，所述胶粘剂组合物中除了以上组分外，还可以包含常规光学丙烯酸酯压敏胶粘剂体系所需的任何必要和非必要组分。
上述胶粘剂组合物用作一种光学胶膜时，该光学胶膜通过以上胶粘剂组合物在光照下固化而成，具体为UV光固化。其中，改性聚合物(B-PAA1或B-PAA2)上的丙烯酸酯基团能与丙烯酸酯单体发生交联反应，进而生成交联固化的光学胶膜，该光学胶膜的分子链中含有硼-氧配位和/或连硼-氧配位键。
本实施例中，所述光学胶膜的透过率大于或等于90％，雾度小于或等于2.0％，剥离力大于或等于1.0N/in，能够满足光学丙烯酸酯胶对光学性能和粘接强度的要求。另外，还可以通过调整改性聚合物(PBDMSA1或PBDMSA2)的分子量以及交联固化程度调控光学胶膜的粘接强度，以满足不同的需求。
实施例3(一种有机硅胶粘剂体系)
本申请又一实施例提供了一种胶粘剂组合物，该胶粘剂组合物包括前述实施例1中的改性聚合物(PBDMS1和/或PBDMS2)和缩合固化型光学有机硅压敏胶粘剂体系的硅氧烷树脂。
进一步地，所述硅氧烷树脂包括烷氧基、酰氧基、酮肟基中的至少一种封端的聚二有机基硅氧烷，所述聚二有机基硅氧烷中的每个有机基独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烃基基团和芳基基团中的任一种。本实施例中，聚二有机基硅氧烷的结构如下式(9)所示：
Figure PCTCN2022138515-appb-000016
其中，n为大于或等于1的整数。
进一步地，所述聚二有机基硅氧烷与所述改性聚合物(PBDMS1和/或PBDMS2)的质量份数之比为(10～80)：(50～90)。本实施例中，所述聚二有机基硅氧烷的弹性模量小于或等于10Mpa，透光率大于或等于90％，雾度小于或等于5.0％。
进一步地，所述胶粘剂组合物还包括催化剂和纳米二氧化硅填料。所述催化剂包括但不限于铂金催化剂。
进一步地，所述胶粘剂组合物还包括纳米二氧化硅填料。
可以理解的，所述胶粘剂组合物中除了以上组分外，还可以包含常规缩合固化型有机硅压敏胶体系所需的任何必要和非必要组分。
上述胶粘剂组合物在湿气条件下固化形成一光学胶膜，其中，改性聚合物(PBDMS1和/或PBDMS2)上的羟基能与聚二有机基硅氧烷上的烷氧基在室温湿气条件下发生缩合反应，最终生成交联固化的光学胶膜，该光学胶膜的分子链中含有硼-氧配位和/或连硼-氧配位键。
具体地，所述改性聚合物(PBDMS1和/或PBDMS2)和式(9)所示的聚二有机基硅氧烷交联反应过程及结构式如下反应式(IX)所示：
Figure PCTCN2022138515-appb-000017
其中，n为大于或等于1的整数。
本实施例中，所述光学胶膜的透过率大于或等于90％，雾度小于或等于2.0％，剥离力大于或等于1.0N/in，能够满足光学有机硅压敏胶粘剂对光学性能和粘接强度的要求。另外，还可以通过调整改性聚合物(PBDMS1或PBDMS2)的分子量以及交联固化程度调控光学胶膜的粘接强度，以满足不同的需求。
本实施例为改性光学有机硅压敏胶粘剂体系，通过在有机硅压敏胶粘剂的分子主链中引入了硼-氧配位键和连硼-氧配位键中的至少一种。由于硼-氧配位键或连硼-氧配位键具有以上独特的断裂与键合行为，使光学有机硅压敏胶粘剂在保证光学胶膜光学性能和粘接性能的前提下具有优异的缓冲、吸能和抗冲击性能，能够吸收外力冲击产生的能力以抵抗冲击作用对面板的影响。另外，通过缩合固化型硅氧烷树脂使含硼-氧配位键或连硼-氧配位键的改性聚合物(PBDMS1和/或PBDMS2)固化成型以形成新结构聚合物，避免含硼-氧配位键或连硼-氧配位键的改性聚合物(PBDMS1和/或PBDMS2)自身容易蠕变流淌且无剥离强度的缺陷。
实施例4(另一中有机硅胶粘剂体系)
本申请又一实施例提供了一种胶粘剂组合物，该胶粘剂组合物包括改性聚合物(PBDMSC)和加成型光学有机硅压敏胶粘剂体系的硅氧烷树脂。所述改性聚合物(PBDMSC)的分子主链中包含硼-氧配位和/或连硼-氧配位键，所述改性聚合物(PBDMSC)的端基和/或侧链中含有乙烯基。
所述改性聚合物(PBDMSC1或PBDMSC2)的结构式分别如式(7)-式(8)所示：
Figure PCTCN2022138515-appb-000018
其中，式(7)-式(8)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团。
进一步地，所述硅氧烷树脂包括聚二有机基硅氧烷，所述聚二有机基硅氧烷的端基和/或侧基含有活泼氢原子，所述聚二有机基硅氧烷中的每个有机基独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烃基基团和芳基基团中的任一种。本实施例中，聚二有机基硅氧烷的结构如下式(10)所示：
Figure PCTCN2022138515-appb-000019
进一步地，所述聚二有机基硅氧烷与所述改性聚合物(PBDMSC1和/或PBDMSC2)的质量份数之比为(10～80)：(50～90)。本实施例中，所述聚二有机基硅氧烷的弹性模量小于或等于10Mpa，透光率大于或等于90％，雾度小于或等于5.0％。
进一步地，所述胶粘剂组合物还包括催化剂和纳米二氧化硅填料。
可以理解的，所述胶粘剂组合物中除了以上组分外，还可以包含常规加成固化型光学有机硅压敏胶体系所需的任何必要和非必要组分。
本实施例中胶粘剂组合物的制备方法具体包括以下步骤：
步骤S41：改性聚合物(PBDMSC1或PBDMSC2)的制备。
该改性聚合物(PBDMSC1或PBDMSC2)是经由前述实施例1中改性聚合物(PBDMS1或PBDMS2)通过乙烯基硅油封端得到，该乙烯基硅油的结构如下式(11)所示：
Figure PCTCN2022138515-appb-000020
前述实施例制备的改性聚合物(PBDMS1或PBDMS2)与乙烯基硅油反应的反应式如下式(X)所示：
Figure PCTCN2022138515-appb-000021
步骤S42，将以上改性聚合物(PBDMSC1和/或PBDMSC2)与式(10)所示的硅氧烷树脂及其他组分混合，以形成所述胶粘剂组合物。
上述胶粘剂组合物在加热条件下固化形成一光学胶膜，其中，改性聚合物(PBDMSC1或PBDMSC2)上的乙烯基基团能与聚二有机基硅氧烷上的活泼氢原子在加热和条件下发生加成聚合反应，最终生成交联固化的光学胶膜，该光学胶膜的分子链中含有硼-氧配位和/或连硼-氧配位键。
具体地，所述改性聚合物(PBDMS1和/或PBDMS2)和式(10)所示的聚二有机基硅氧烷交联反应过程及结构式如下反应式(XI)所示：
Figure PCTCN2022138515-appb-000022
本实施例中，所述光学胶膜的透过率大于或等于90％，雾度小于或等于2.0％，剥离力大于或等于1.0N/in，能够满足光学有机硅压敏胶粘剂对光学性能和粘接强度的要求。另外，还可以通过调整改性聚合物(PBDMS1和/或PBDMS2)的分子量以及交联固化程度调控光学胶膜的粘接强度，以满足不同的需求。
本实施例为另一种改性光学有机硅压敏胶粘剂体系，通过在有机硅压敏胶粘剂的分子主链中引入了硼-氧配位键和连硼-氧配位键中的至少一种。由于硼-氧配位键或连硼-氧配位键具有以上独特的断裂与键合行为，使光学有机硅压敏胶粘剂在保证光学胶膜光学性能和粘接性能的前提下具有优异的缓冲、吸能和抗冲击性能，能够吸收外力冲击产生的能力以抵抗冲击作用对面板的影响。另外，通过加成固化型硅氧烷树脂可以使改性聚合物(PBDMSC1和/或PBDMSC2)固化成型，形成新结构聚合物避免含硼的改性聚合物(PBDMSC1和/或PBDMSC2)容易蠕变流淌且无剥离强度的缺陷。
实施例5(环氧树脂胶粘剂体系)
本申请又一实施例提供了一胶粘剂组合物，该胶粘剂组合物包括前述实施例1中的改性聚合物(PBDMS1和/或PBDMS2)和环氧树脂。
进一步地，所述环氧树脂可以是任何环氧树脂，具体可以为双酚A型环氧树脂、双酚F型环氧树脂中的至少一种。
进一步地，所述胶粘剂组合物还包括交联剂，该叔胺交联剂包括但不限于酸酐类、胺类、双氰胺等。
进一步地，所述环氧树脂与所述改性聚合物的质量份数之比为(10～30)：(30～60)。
可以理解的，所述胶粘剂组合物中除了以上组分外，还可以包含常规光学环氧树脂压敏胶粘剂体系所需的任何必要和非必要组分。
本实施例还提供一种光学胶膜，所述光学胶膜是将上述胶粘剂组合物在加热条件下固化形成，改性聚合物(PBDMS1或PBDMS2)上的羟基能与环氧树脂的环氧基团在加热和条件下发生聚合反应，最终生成交联固化的光学胶膜，该光学胶膜的分子链中含有硼-氧配位和/或连硼-氧配位键。
具体地，所述改性聚合物(PBDMS1或PBDMS2)中的及与环氧树脂的环氧基团交联反应过程及结构式如下反应式(XII)-反应式(XIII)所示：
Figure PCTCN2022138515-appb-000023
其中，反应式(XII)-反应式(XIII)中的R分别为双酚A或双酚F的残基；每个n均为大于或等于1的整数，本实施例中所述改性聚合物(PBDMS1或PBDMS2)中R1和R2均为甲基。
可以理解的，反应式(XII)-反应式(XIII)得到的环氧树脂胶粘剂产物为线型结构，为液态，还可以添加其他填料(例如纳米二氧化硅、增塑剂等)在酸酐类或胺类等固化剂的作 用下进一步交联固化，形成交联网状结构。
本实施例中，所述光学胶膜的透过率大于或等于90％，雾度小于或等于2.0％，剥离力大于或等于1.0N/in，能够满足光学环氧树脂压敏胶粘剂对光学性能和粘接强度的要求。另外，还可以通过调整改性聚合物(PBDMS1和/或PBDMS2)的分子量以及交联固化程度调控光学胶膜的粘接强度，以满足不同的需求。
本实施例为改性光学环氧树脂压敏胶粘剂体系，通过在环氧树脂压敏胶粘剂的分子主链中引入了硼-氧配位键和连硼-氧配位键中的至少一种。由于硼-氧配位键或连硼-氧配位键具有以上独特的断裂与键合行为，使光学环氧树脂压敏胶粘剂在保证光学胶膜光学性能和粘接性能的前提下具有优异的缓冲、吸能和抗冲击性能，能够吸收外力冲击产生的能力以抵抗冲击作用对面板的影响。
请参阅图1，本申请还提供了一种折叠屏100，该折叠屏100包括面板10、叠设于所述面板10正面的多层基材层20和光学胶膜30，其中面板10和与之相邻的基材层20、以及相邻两层基材层20之间均设有一层光学胶膜30。所述光学胶膜30采用前述任意一种胶粘剂组合物经固化而成。根据前述不同胶粘剂组合物，采用的固化方式不同。
进一步地，所述折叠屏100可以通过以下两种工艺制备而成。
第一种工艺为：制备前述任意一种胶粘剂组合物，将该胶粘剂组合物进行真空脱泡；将脱泡后的胶粘剂组合物涂布于基材层20上，并进行固化得到光学胶膜30；于光学胶膜30的表面覆盖离型膜，从而制备单面光学胶带，并将单面光学胶带进行模切；将模切好的单面光学胶带去掉离型膜后贴合于面板10的正面，若需要贴合多层基材层20，可以依次贴合单面光学胶带，再次进行脱泡，得到所述折叠屏100。可以理解的，当需要贴合多层基材层20时，可以将位于中间的基材层20的两表面均涂布胶粘剂组合物以制备双面光学胶带。还可以理解的是，可以根据实际产品抗冲击性能的需要，设计不同层数和不同厚度的光学胶膜30。还可以理解的，当需要贴合多层基材层20时，所述折叠屏100还可以包括常规光学胶膜。
第二种工艺为：制备前述任意一种胶粘剂组合物，将该胶粘剂组合物进行真空脱泡；将脱泡后的胶粘剂组合物点涂或喷涂于面板10的正面形成未固化的胶膜(图未示)，再将基材层20贴合于未固化的胶膜的表面，再次进行真空脱泡，脱泡后进行固化得到光学胶膜30，若需要贴合多层基材层20，可以重复上述方法依次形成多层光学胶膜30，从而获得所述折叠屏100。此工艺为先叠层后固化工艺，可以应用于局部粘接的情况，无需大面积布胶，操作更灵活。
进一步地，所述基材层20的材料包括但不限于PI或PET。
光学胶膜30的分子主链中引入了硼氧配位键和连硼氧配位键，由于硼-氧配位键或连硼-氧配位键具有前述独特的断裂与键合行为，在受到冲击作用时，能够吸收能量以抵抗冲击作用对胶膜的影响，使光学胶膜30在维持优良的粘接性能和光学性能的前提下具有优异的抗冲击性能。多层光学胶膜30结合多层基材层20可以很好地抵抗外力冲击，提高折叠屏的抗冲击性能，降低外力冲击使面板10出现黑斑或者碎亮点等失效现象。
下面通过具体实施例对本申请实施例进行进一步的说明。
合成例一
一种硼氧键改性的端羟基硅油聚合物(PBDMS1或PBDMS2)的制备：
合成硼氧键改性的端羟基硅油聚合物(PBDMS1或PBDMS2)的原料配方如表1所示。
表1
Figure PCTCN2022138515-appb-000024
将表1中配方按照相应比例加入反应容器中(例如烧杯、烧瓶、反应釜等)，在室温下，以5-5000rpm的转速搅拌≥2h，搅拌过程中真空度-0.08Mpa～-0.095Mpa。直到混合均匀(具体表现为均匀分散，无颗粒沉降，无分相)，将反应环境升温至50～100℃，保持搅拌速度和真空度，反应时间≥4h，得到PBDMS1或PBDMS2。
合成例二
一种改性硅油聚合物(PBDMSA1或PBDMSA2)的制备：
合成改性硅油聚合物(PBDMSA1或PBDMSA2)的原料配方如表2所示。
表2
原料 典型类型/牌号 质量份数
PBDMS1或PBDMS2 合成例一 40-70
异氰酸酯丙烯酸乙酯 AOI 15-25
溶剂 甲醇、甲苯、THF、乙酸乙酯等 5-40
有机锡催化剂 DBTDL二月桂酸二丁基锡等 0-5
阻聚剂 对苯二酚HQ、苯醌PBQ等 0-1
将表2中PBDMS1或PBDMS2、溶剂、催化剂、阻聚剂按照比例加入反应容器中(烧杯、烧瓶、反应釜等)，通氮气，以5～5000rpm的转速将原料搅拌均匀并升温60～100℃，搅拌时间≥1h，然后按照比例加入异氰酸酯丙烯酸乙酯和有机锡催化剂开始反应，保证反应时间≥1h，之后停氮气，抽真空(真空度-0.08Mpa～-0.095Mpa)以5～5000rpm转速搅拌2小时以上，直至溶剂挥发完全，过滤得到PBDMSA1或PBDMSA2。
合成例三
一种改性丙烯酸酯聚合物(B-PAA1或B-PAA2)的制备：
合成改性丙烯酸酯聚合物(B-PAA1或B-PAA2)的原料配方如表3所示。
表3
Figure PCTCN2022138515-appb-000025
将表3中配方按照相应比例加入反应容器中(例如烧杯、烧瓶、反应釜等)，在室温下，以5～5000rpm的转速搅拌≥2h，搅拌过程中真空度-0.08Mpa～-0.095Mpa。直到混合均匀(具体表现为均匀分散，无颗粒沉降，无分相)，将反应环境升温至60～100℃，保持搅拌速度和真空度，反应时间≥4h。再按照比例加入丙烯酸羟乙酯或者丙烯酸羟丁酯，保持反应温度60～100℃，搅拌速度5～5000rpm、时间≥4h和真空度-0.08Mpa～-0.095Mpa，直到反应完成，得到改性丙烯酸酯聚合物(B-PAA1或B-PAA2)。
合成例四
一种改性硅油聚合物(PBDMSC1或PBDMSC2)的制备：
合成改性硅油聚合物(PBDMSC1或PBDMSC2)的原料配方如表4所示。
表4
原料 典型类型/牌号 质量份数
PBDMS1或PBDMS2 合成例一 40-70
乙烯基硅油 式10 15-25
溶剂 甲醇、甲苯、THF、乙酸乙酯等 5-40
催化剂 氢氧化锂 0-5
将表4中PBDMS1或PBDMS2、乙烯基硅油、溶剂、催化剂按照比例加入反应容器中(烧杯、烧瓶、反应釜等)，常温下反应得到PBDMSC1或PBDMSC2。
实施例一
一种丙烯酸酯体系的胶粘剂组合物的制备：
合成胶粘剂组合物的原料配方如表5所示。
表5
原料 典型类型/牌号 质量份数
PBDMSA1和/或PBDMSA2 合成例二 30-80
丙烯酸酯单体 丙烯酸丁酯、丙烯酸月桂酯等 20-50
光引发剂 184、TPO等 0-5
抗氧剂 抗氧剂1010、抗氧剂DNP等 0-5
增塑剂 DMP、DOP等 0-30
将以上PBDMSA1和/或PBDMSA2与丙烯酸酯单体、光引发剂、抗氧剂和增塑剂按以上比例混合均匀，得到丙烯酸酯体系的胶粘剂组合物，待用。
实施例二
另一种丙烯酸酯体系的胶粘剂组合物的制备：
合成另一种丙烯酸酯体系的胶粘剂组合物的原料配方如表6所示。
表6
原料 典型类型/牌号 质量份数
B-PAA1和/或B-PAA2 合成例三 30-80
丙烯酸酯单体 丙烯酸丁酯、丙烯酸月桂酯等 0-70
光引发剂 184、TPO等 0-5
抗氧剂 抗氧剂1010、抗氧剂DNP等 0-5
增塑剂 DMP、DOP等 0-50
将以上B-PAA1和/或B-PAA2与丙烯酸酯单体、光引发剂、抗氧剂和增塑剂按以上比例混合均匀，得到丙烯酸酯体系的胶粘剂组合物，待用。
实施例三
(1)一种有机硅体系的胶粘剂组合物的制备：
制备有机硅体系的胶粘剂组合物的原料配方如表7所示。
表7
Figure PCTCN2022138515-appb-000026
将表7中实施例一制备的PBDMS1和/或PBDMS2、缩合固化型有机硅胶粘剂、纳米二氧化硅填料、催化剂和溶剂按以上照比例混合均匀得到一种有机硅体系的胶粘剂组合物。
(2)一种有机硅体系的液态光学固化胶粘结的制备：
再将(1)得到的胶粘剂组合物加入反应容器中(烧杯、烧瓶、反应釜等)，抽真空，以5-5000rpm的转速将原料搅拌均匀并升温≥60℃，搅拌过程中真空度≥-200kpa反应时间≥1h，得到另一种有机硅体系的液态光学胶粘剂，待用。
实施例四
(1)另一种有机硅体系的胶粘剂组合物的制备：
制备另一种有机硅体系的胶粘剂组合物的原料配方如表8所示。
表8
Figure PCTCN2022138515-appb-000027
将表8中PBDMSC1和/或PBDMSC2与端基中含有氢原子的聚二甲基硅氧烷、纳米二氧化硅填料、催化剂和溶剂按照比例混合均匀得到另一种有机硅体系的胶粘剂组合物。
(2)另一种有机硅体系的液态光学固化胶粘结的制备：
再将(1)得到的胶粘剂组合物加入反应容器中(烧杯、烧瓶、反应釜等)，抽真空，以5-5000rpm的转速将原料搅拌均匀并升温≥60℃，搅拌过程中真空度≥-200kpa反应时间≥1h，得到另一种有机硅体系的液态光学固化胶粘结，待用。
实施例五
(1)一种环氧树脂体系的胶粘剂组合物的制备：
制备环氧树脂体系的胶粘剂组合物的原料配方如表9所示。
表9
Figure PCTCN2022138515-appb-000028
将表9中实施例一合成的PBDMS1和/或PBDMS2、环氧树脂和交联剂按照比例混合均匀得到环氧树脂体系的胶粘剂组合物。
(2)一种环氧树脂体系的液态光学胶粘剂的制备：
将(1)制备环氧树脂体系的胶粘剂组合物加入反应容器中(烧杯、烧瓶、反应釜等)，抽真空，以5-5000rpm的转速将原料搅拌均匀并升温≥60℃，搅拌过程中真空度≥-200kpa反应时间≥1h，得到所述环氧树脂体系的液态光学胶粘剂，待用。
(3)一种交联网状结构环氧树脂胶粘剂的制备：
将(2)制备的线型环氧树脂胶粘剂按如下表10所示的配方混合并进一步固化得到交联网状的胶粘剂。
表10
Figure PCTCN2022138515-appb-000029
实施例六
一种折叠屏：
在面板的正面层叠两层PI基材和两层光学胶膜，两层光学胶膜分别位于面板和PI基材之间以及两层PI基材之间，其中，PI基材厚度50μm，光学胶膜厚度50μm，所述光学胶膜为本申请实施例三制备的连硼-氧配位键改性有机硅胶粘剂体系的光学胶膜。
对比例一
一种现有折叠屏：
在面板的正面层叠两层PI基材和两层光学胶膜，两层光学胶膜分别位于面板和PI基材之间以及两层PI基材之间，其中，PI基材厚度50μm，光学胶膜厚度50μm，光学胶膜为现有有机硅胶粘剂体系的光学胶膜。
使用本申请实施例三制备的连硼-氧配位键改性有机硅胶粘剂制备折叠屏，进行钢球冲击试验，钢球重量为32g，直径20mm，钢球测试如图2所示，测试两种折叠屏在钢球冲击下出现碎亮点的失效高度，测试结果如图3所示，对比例一的折叠屏出现碎亮点的最低失效高度为73cm，本申请实施例六的折叠屏从出现碎亮点的最低失效高度为91cm，相较于对比例一有明显的提升。说明本申请在光学胶膜的分子主链中引入了硼氧配位键和连硼氧配位键，由于硼-氧配位键或连硼-氧配位键具有前述独特的断裂与键合行为，在受到冲击作用时，能够吸收能量以抵抗冲击作用对胶膜的影响，使光学胶膜在维持优良的粘接性能和光学性能的前提下具有优异的抗冲击性能。多层光学胶膜结合多层基材层可以很好地抵抗外力冲击，提高折叠屏的抗冲击性能，降低外力冲击使面板出现黑斑或者碎亮点等失效现象。
需要说明的是，以上仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本申请的保护范围之内；在不冲突的情况下，本申请的实施方式及实施方式中的特征可以相互组合。因此，本申请的保护范围应以权利要求的保护范围为准。

Claims (26)

  1. 一种胶粘剂组合物，其特征在于，包括：
    胶粘剂基体；以及
    改性聚合物，
    其中，所述改性聚合物的主链中包含硼-氧配位和/或连硼-氧配位键，所述改性聚合物的端基和/或侧链包含羟基、丙烯酸酯基、乙烯基中的至少一种。
  2. 根据权利要求1所述的胶粘剂组合物，其特征在于，所述改性聚合物的结构式为式(1)-式(2)，式(1)-式(2)的结构如下所示：
    Figure PCTCN2022138515-appb-100001
    其中，式(1)-式(2)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团；
    所述胶粘剂基体包括硅氧烷树脂和环氧树脂中的至少一种。
  3. 根据权利要求2所述的胶粘剂组合物，其特征在于，所述硅氧烷树脂包括烷氧基、酰氧基、酮肟基中的至少一种封端的聚二有机基硅氧烷，所述聚二有机基硅氧烷中的每个有机基独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烃基基团和芳基基团中的任一种；
    所述环氧树脂包括双酚A型环氧树脂和双酚F型环氧树脂中的至少一种。
  4. 根据权利要求2或3所述的胶粘剂组合物，其特征在于，所述胶粘剂基体与所述改性聚合物的质量份数之比为(10～80)：(50～90)或(10～30)：(50～90)。
  5. 根据权利要求1所述的胶粘剂组合物，其特征在于，所述改性聚合物的结构式为式(3)-式(6)，式(3)-式(6)的结构如下所示：
    Figure PCTCN2022138515-appb-100002
    其中，式(3)-式(6)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团；
    所述胶粘剂基体包括丙烯酸酯单体。
  6. 根据权利要求5所述的胶粘剂组合物，其特征在于，所述改性聚合物与所述丙烯酸酯单体的质量份数之比为(30～80)：(20～50)或(30～80)：(0.1～70)。
  7. 根据权利要求1所述的胶粘剂组合物，其特征在于，所述改性聚合物的结构式为式(7)-式(8)，式(7)-式(8)的结构如下所示：
    Figure PCTCN2022138515-appb-100003
    其中，式(7)-式(8)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团；
    所述胶粘剂基体包括硅氧烷树脂。
  8. 根据权利要求7所述的胶粘剂组合物，其特征在于，所述硅氧烷树脂包括聚二有机基硅氧烷，所述聚二有机基硅氧烷的端基和/或侧基含有活泼氢原子，所述聚二有机基硅氧烷中的每个有机基独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烃基基团和芳基基团中的任一种。
  9. 根据权利要求7或8所述的胶粘剂组合物，其特征在于，所述胶粘剂基体与所述改性聚合物的质量份数之比为(10～80)：(50～90)。
  10. 一种胶粘剂组合物的制备方法，其特征在于，包括：将胶粘剂基体与改性聚合物混合得到所述胶粘剂组合物，其中，所述改性聚合物的主链中包含硼-氧配位和/或连硼-氧配位键，所述改性聚合物的端基和/或侧链包含羟基、丙烯酸酯基、乙烯基中的至少一种。
  11. 根据权利要求10所述的制备方法，其特征在于，所述改性聚合物通过端羟基硅油与硼酸和/或二硼酸反应得到，所述改性聚合物的结构式为式(1)-式(2)，式(1)-式(2)的结构如下所示：
    Figure PCTCN2022138515-appb-100004
    其中，式(1)-式(2)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团；
    所述胶粘剂基体包括硅氧烷树脂和环氧树脂中的至少一种。
  12. 根据权利要求11所述的制备方法，其特征在于，所述端羟基硅油包括三种分子量的端羟基硅油，三种分子量的所述端羟基硅油的粘度分别为大于或等于15000cps、4000～15000cps以及小于或等于4000cps。
  13. 根据权利要求12所述的制备方法，其特征在于，粘度分别为大于或等于15000cps、 4000～15000cps以及小于或等于4000cps的所述端羟基硅油的质量份数之比为(30～60)：(20～50)：(20～30)；
    所述硼酸和/或二硼酸的总的质量份数为0.1～5。
  14. 根据权利要求11至13任意一项所述的制备方法，其特征在于，所述硅氧烷树脂包括烷氧基、酰氧基、酮肟基中的至少一种封端的聚二有机基硅氧烷，所述聚二有机基硅氧烷中的每个有机基独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烃基基团和芳基基团中的任一种；
    所述环氧树脂包括双酚A型环氧树脂和双酚F型环氧树脂中的至少一种。
  15. 根据权利要求11至14任意一项所述的制备方法，其特征在于，所述胶粘剂基体与所述改性聚合物的质量份数之比为(10～80)：(50～90)或(10～30)：(50～90)。
  16. 根据权利要求10所述的制备方法，其特征在于，所述改性聚合物通过端羟基硅油与硼酸和/或二硼酸反应得到中间体，再通过所述中间体与异氰酸酯丙烯酸酯反应得到，所述改性聚合物的结构式为式(3)-式(4)，式(3)-式(4)的结构如下所示：
    Figure PCTCN2022138515-appb-100005
    其中，式(3)-式(4)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团；
    所述胶粘剂基体包括丙烯酸酯单体。
  17. 根据权利要求16所述的制备方法，其特征在于，所述改性聚合物与所述丙烯酸酯单体的质量份数之比为(30～80)：(20～50)。
  18. 根据权利要求10所述的制备方法，其特征在于，所述改性聚合物通过端羟基丙烯酸酯聚合物与硼酸和/或二硼酸反应生成中间体，在通过所述中间体与羟基丙烯酸单体反应得到，所述改性聚合物的结构式为式(5)-式(6)，式(5)-式(6)的结构如下所示：
    Figure PCTCN2022138515-appb-100006
    其中，式(5)-式(6)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团，n为大于或等于1的整数；
    所述胶粘剂基体包括丙烯酸酯单体。
  19. 根据权利要求18所述的制备方法，其特征在于，所述改性聚合物与所述丙烯酸酯单体的质量份数之比为(30～80)：(0.1～70)。
  20. 根据权利要求10所述的制备方法，其特征在于，所述改性聚合物通过端羟基丙烯酸酯聚合物与硼酸和/或二硼酸反应生成中间体，在通过所述中间体与乙烯基硅油反应得到，所述改性聚合物的结构式为式(7)-式(8)，式(7)-式(8)的结构如下所示：
    Figure PCTCN2022138515-appb-100007
    其中，式(7)-式(8)中的R 1，R 2分别独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烷基基团和芳基组成的组中的基团；
    所述胶粘剂基体包括硅氧烷树脂。
  21. 根据权利要求20所述的制备方法，其特征在于，所述硅氧烷树脂包括聚二有机基硅氧烷，所述聚二有机基硅氧烷的端基和/或侧基含有活泼氢原子，所述聚二有机基硅氧烷中的每个有机基独立地选自自由烷基基团、自由烷氧基基团、链烯基基团、环烃基基团和芳基基团中的任一种。
  22. 根据权利要求20或21所述的制备方法，其特征在于，所述胶粘剂基体与所述改性聚合物的质量份数之比为(10～80)：(50～90)。
  23. 一种光学胶膜，其特征在于，由权利要求1至9中任意一项所述的胶粘剂组合物固化而成，所述光学胶膜的分子链中包含硼-氧配位和/或连硼-氧配位键。
  24. 根据权利要求23所述的光学胶膜，其特征在于，所述光学胶膜的透过率大于或等于90％，雾度小于或等于2.0％，剥离力大于或等于1.0N/in。
  25. 一种折叠屏，其特征在于，包括面板以及叠设于所述面板的表面的至少一层基材层和至少一层光学胶膜，所述面板和与之相邻的所述基材层之间、以及相邻两所述基材层之间均设有一层所述光学胶膜，所述光学胶膜为权利要求23或24所述的光学胶膜。
  26. 一种电子设备，其特征在于，包括权利要求23或24所述的光学胶膜，或权利要求25所述的折叠屏。
PCT/CN2022/138515 2021-12-20 2022-12-13 胶粘剂组合物及其制备方法、光学胶膜及其应用 WO2023116494A1 (zh)

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