WO2020042885A1 - 光学胶及其制造方法、显示装置 - Google Patents

光学胶及其制造方法、显示装置 Download PDF

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Publication number
WO2020042885A1
WO2020042885A1 PCT/CN2019/099661 CN2019099661W WO2020042885A1 WO 2020042885 A1 WO2020042885 A1 WO 2020042885A1 CN 2019099661 W CN2019099661 W CN 2019099661W WO 2020042885 A1 WO2020042885 A1 WO 2020042885A1
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Prior art keywords
adhesive layer
adhesive
layer
mixture
storage modulus
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PCT/CN2019/099661
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English (en)
French (fr)
Inventor
杜双
蔡宝鸣
张家豪
刘运进
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京东方科技集团股份有限公司
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Priority to US16/640,113 priority Critical patent/US11008484B1/en
Publication of WO2020042885A1 publication Critical patent/WO2020042885A1/zh

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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
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/841—Self-supporting sealing arrangements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C09J2301/1242—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape the opposite adhesive layers being different
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
    • 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
    • C09J2301/312—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 parameters being the characterizing feature
    • 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
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/0412—Digitisers structurally integrated in a display
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/311—Flexible OLED
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/40—OLEDs integrated with touch screens
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • Embodiments of the present disclosure relate to an optical glue, a manufacturing method thereof, and a display device.
  • the display device usually includes a display panel, and may further include components such as a touch structure (such as a touch screen), a polarizer, and a protective structure (such as a cover layer).
  • a touch structure such as a touch screen
  • a polarizer such as a polarizer
  • a protective structure such as a cover layer.
  • Each of the above-mentioned components is bonded together by, for example, an optical adhesive.
  • Optical adhesive is a special adhesive for bonding transparent optical components. It has the characteristics of colorless and transparent, high light transmittance, and good bonding strength. Optical glue can bond various components in a display device, and it does not affect the normal display while achieving the bonding function. It is one of the important raw materials in a display device.
  • At least one embodiment of the present disclosure provides an optical adhesive including a first adhesive layer, a second adhesive layer, and a third adhesive layer that are sequentially stacked, wherein a storage modulus of the first adhesive layer is greater than that of the third adhesive.
  • the storage modulus of the layer, and the storage modulus of the first adhesive layer and the storage modulus of the third adhesive layer are both greater than the storage modulus of the second adhesive layer.
  • the storage modulus of the first glue layer is 50KPa-200KPa.
  • the storage modulus of the second glue layer is 15KPa-80KPa.
  • the storage modulus of the third glue layer is 30KPa-100KPa.
  • the glass transition temperature of the optical adhesive is less than -30 ° C.
  • the thickness of the first adhesive layer is 2 ⁇ m-30 ⁇ m
  • the thickness of the second adhesive layer is 5 ⁇ m-100 ⁇ m
  • the thickness of the third adhesive layer is 2 ⁇ m -100 ⁇ m.
  • the optical adhesive provided in an embodiment of the present disclosure further includes: a first release film disposed on a side of the first adhesive layer away from the second adhesive layer; a second release film disposed on the first adhesive layer
  • the third adhesive layer is on a side far from the second adhesive layer.
  • the transmittances of the first glue layer, the second glue layer, and the third glue layer are all greater than 93%, and the first glue layer, The haze of the second glue layer and the third glue layer is less than 1%.
  • At least one embodiment of the present disclosure further provides a display device including a display panel and a cover layer disposed in a stacked manner, wherein an adhesive film is provided between the display panel and the cover layer, and the adhesive film includes the present disclosure
  • a side of the first glue layer of the optical glue remote from the second glue layer is subjected to a compressive stress when the display device is bent.
  • the cover layer when the display device is bent, the cover layer is located outside the display panel, the first adhesive layer is in contact with the cover layer, and the The third adhesive layer is in contact with the display panel.
  • the display panel is a flexible organic light emitting diode display panel.
  • a display device provided in an embodiment of the present disclosure further includes a polarizer, wherein the polarizer is disposed between the display panel and the cover layer, and between the display panel and the polarizer, The adhesive film is provided between the polarizer and the cover layer.
  • a display device provided in an embodiment of the present disclosure further includes a touch structure layer, wherein the touch structure layer is sandwiched between the polarizer and the cover layer, and the polarizer and the cover The adhesive film is provided between the touch structure layers and between the touch structure layer and the cover layer.
  • the display device is configured to bend with a curvature radius of 1 mm-6 mm.
  • At least one embodiment of the present disclosure also provides a method for manufacturing an optical adhesive, comprising: applying a first mixture to a first release film, curing the first mixture to form a first adhesive layer; and applying a second mixture to the first adhesive layer. Covering the first mixture, curing the second mixture to form a second glue layer; applying a third mixture to the second mixture, and curing the third mixture to form a third glue layer; ,
  • the storage modulus of the first adhesive layer is greater than the storage modulus of the third adhesive layer, and the storage modulus of the first adhesive layer and the storage modulus of the third adhesive layer are both Greater than the storage modulus of the second glue layer.
  • the first adhesive layer, the second adhesive layer, and the third adhesive layer are formed in a same curing process, or are cured independently of each other. Formed in the process.
  • the method for manufacturing an optical adhesive provided in an embodiment of the present disclosure further includes: providing a second release film, and covering the second release film to the third adhesive layer away from the second adhesive layer. One side.
  • each of the first mixture, the second mixture, and the third mixture includes a monomer mixture, an initiator, and a crosslinking agent.
  • each of the first mixture, the second mixture, and the third mixture further includes organic nanoparticles.
  • the ratios of initiator ratios of the first mixture, the second mixture, and the third mixture are different, so that the first glue layer And the storage modulus of the first adhesive layer and the storage modulus of the third adhesive layer are both larger than the second adhesive layer. Storage modulus.
  • the first mixture in a curing process of forming the first adhesive layer, the second adhesive layer, and the third adhesive layer, respectively, the first mixture
  • the reaction rates of the second mixture and the third mixture are different, so that the storage modulus of the first glue layer is greater than the storage modulus of the third glue layer, and the first glue layer And the storage modulus of the third adhesive layer are both larger than the storage modulus of the second adhesive layer.
  • FIG. 1 is a schematic diagram of a layer structure of an optical adhesive provided by at least one embodiment of the present disclosure
  • FIG. 2 is a schematic diagram of a layer structure of another optical adhesive provided by at least one embodiment of the present disclosure
  • FIG. 3 is a schematic diagram of a layer structure of a display device provided by at least one embodiment of the present disclosure
  • FIG. 4 is a schematic diagram of a layer structure of another display device in a bent state according to at least one embodiment of the present disclosure
  • FIG. 5 is a schematic simulation diagram of the strain of each film layer of the display device shown in FIG. 4 in a bent state
  • FIG. 6 is a schematic flowchart of a method for manufacturing an optical adhesive according to at least one embodiment of the present disclosure.
  • FIG. 7 is a schematic diagram of a process of an optical adhesive provided by at least one embodiment of the present disclosure.
  • the flexible display device can be bent or folded, and is suitable for various application scenarios, which effectively improves the user experience.
  • a flexible display device generally includes a flexible display panel and a plurality of external members, and these components are bonded to each other through an optical glue.
  • the strain of the flexible display panel and the external member is caused by any one of compressive stress or tensile stress. Due to the effects of stress, various components in the flexible display device may have problems such as wrinkles, fractures, separation, and other film failures. Therefore, in a flexible display device, a stress control member (ie, a neutral layer) needs to be provided, so that each component has a smaller deformation amount during the bending process.
  • the stress control member is usually an optical adhesive, and the conventional optical adhesive has limited stress control effect, which is difficult to meet the application requirements.
  • At least one embodiment of the present disclosure provides an optical adhesive, a method for manufacturing the same, and a display device.
  • the optical adhesive not only has a strong bonding ability, but also can reduce the bending stress of the components to which it is attached, and can suppress the generation of air bubbles. Avoid the problem of film failure such as wrinkles, fractures and separation.
  • At least one embodiment of the present disclosure provides an optical adhesive including a first adhesive layer, a second adhesive layer, and a third adhesive layer that are sequentially stacked.
  • the storage modulus of the first glue layer is greater than the storage modulus of the third glue layer, and both the storage modulus of the first glue layer and the storage modulus of the third glue layer are greater than the storage modulus of the second glue layer. the amount.
  • FIG. 1 is a schematic diagram of a layer structure of an optical adhesive provided by at least one embodiment of the present disclosure.
  • the optical adhesive 100 includes a first adhesive layer 110, a second adhesive layer 120, and a third adhesive layer 130 that are sequentially stacked.
  • the storage modulus of each glue layer is different.
  • the storage modulus of the first adhesive layer 110 is greater than the storage modulus of the third adhesive layer 130, and the storage modulus of the first adhesive layer 110 and the storage modulus of the third adhesive layer 130 are both greater than the second The storage modulus of the adhesive layer 120.
  • the storage modulus of the first adhesive layer 110 is the largest, the storage modulus of the second adhesive layer 120 is the smallest, and the storage modulus of the third adhesive layer 130 is between the first Between the storage modulus of the adhesive layer 110 and the storage modulus of the second adhesive layer 120.
  • the storage modulus of each rubber layer is positively related to hardness, that is, the larger the storage modulus, the greater the hardness.
  • the storage modulus represents the material's ability to store elastic deformation energy and is an indicator of the material's rebound after deformation.
  • the storage modulus of the first adhesive layer 110 is 50KPa-200KPa, for example, it may be further 50KPa-100KPa.
  • the storage modulus of the second adhesive layer 120 is 15KPa-80KPa, for example, it may be further 15KPa-50KPa.
  • the storage modulus of the third adhesive layer 130 is 30KPa-100KPa. The storage modulus of each of the above adhesive layers was measured at a frequency of 1 Hz.
  • the glass transition temperature of the optical adhesive 100 is less than -30 ° C, for example, it may be further lower than -40 ° C, so that the display device using the optical adhesive 100 has better folding performance at low temperature.
  • the use temperature of the optical adhesive 100 may be -30 ° C to 70 ° C, for example, it may be further -40 ° C to 85 ° C.
  • the thickness of the first adhesive layer 110 is 2 ⁇ m to 30 ⁇ m, for example, it may be further 2 ⁇ m to 25 ⁇ m or 2 ⁇ m to 10 ⁇ m.
  • the thickness of the second adhesive layer 120 is 5 ⁇ m to 100 ⁇ m, for example, it may be further 5 ⁇ m to 50 ⁇ m.
  • the thickness of the third adhesive layer 130 is 2 ⁇ m to 100 ⁇ m, for example, it may be further 5 ⁇ m to 25 ⁇ m.
  • the thickness of the first adhesive layer 110 and the third adhesive layer 130 may be the same or different, which may be based on factors such as the interface where the first adhesive layer 110 and the third adhesive layer 130 are in contact with each other, and the position in the stacked structure. It depends.
  • the light transmittances of the first adhesive layer 110, the second adhesive layer 120, and the third adhesive layer 130 are all greater than 93%, and the haze of the first adhesive layer 110, the second adhesive layer 120, and the third adhesive layer 130 are all less than 1%.
  • the optical adhesive 100 is bonded between other components provided separately.
  • a suitable laminating direction when the component attached to the optical adhesive 100 is bent or folded, the side of the first adhesive layer 110 away from the second adhesive layer 120 is subjected to compressive stress (that is, the first adhesive layer 110 and the The side where the other parts touch is subjected to compressive stress). Since the storage modulus of the first adhesive layer 110 is the largest among the three adhesive layers, the first adhesive layer 110 can withstand a large compressive stress, thereby effectively suppressing the generation of bubbles caused by bending or high temperature, and Can avoid wrinkles.
  • the first adhesive layer 110 and the third adhesive layer 130 each have a large storage modulus, high viscosity, strong adhesive ability, and can be better bonded with other components.
  • the storage modulus of the second adhesive layer 120 is the smallest, which can allow a large shear slip and shear strain between the film layers, thereby reducing the Bending stress can effectively suppress the generation of air bubbles and avoid the problems of film failure such as wrinkles, fractures, and separation.
  • the optical adhesive 100 is not limited to the three-layer structure composed of the first adhesive layer 110, the second adhesive layer 120, and the third adhesive layer 130, and may also be any multilayer structure, such as , 4 layers, 5 layers, etc., for example, the side where the glue layer with the largest storage modulus in the multilayer structure is in contact with other parts that are separately provided is subjected to compressive stress during bending, and the glue in contact with other parts in the multilayer structure
  • the storage modulus of the layer is greater than the storage modulus of the glue layer in the multilayer structure that is not in contact with other components.
  • a fourth adhesive layer may be added between the first adhesive layer 110 and the second adhesive layer 120, and the storage modulus of the fourth adhesive layer is between that of the first adhesive layer 110 and the second adhesive layer 120. And can be larger or smaller than the storage modulus of the third adhesive layer 130; on this basis, a fifth adhesive layer can also be added between the second adhesive layer 120 and the third adhesive layer 130, the fifth The storage modulus of the adhesive layer is between the storage modulus of the second adhesive layer 120 and the third adhesive layer 130, and may be larger or smaller than that of the fourth adhesive layer.
  • FIG. 2 is a schematic diagram of a layer structure of another optical adhesive provided by at least one embodiment of the present disclosure.
  • the optical glue 100 of this embodiment is basically the same as the optical glue 100 shown in FIG. 1.
  • the first release film 141 is disposed on a side of the first adhesive layer 110 away from the second adhesive layer 120; the second release film 142 is disposed on a third of the third adhesive layer 130 away from the second adhesive layer 120. side.
  • the first release film 141 covers the surface where the first adhesive layer 110 is to be attached to other components
  • the second release film 142 covers the surface where the third adhesive layer 130 is to be attached to other components, and is to be attached to the first adhesive layer 110.
  • the other components to be bonded are different from the other components to be bonded to the third adhesive layer 130.
  • the first release film 141 and the second release film 142 can play a protective role to prevent the first adhesive layer 110, the second adhesive layer 120, and the third adhesive layer 130 from being damaged before being bonded to other components, and are convenient for collection. Roll, store and transport.
  • the first release film 141 and the second release film 142 may be PET (Polyethylene Terephthalate) release films, and the first release film 141 is a heavy release film, and the second release film 142 is a light release film.
  • the release force, thickness, and other parameters of the first release film 141 and the second release film 142 can be determined according to actual needs, so as to have a good peeling effect, and the first adhesive layer will not be caused when peeling. 110, the second adhesive layer 120 and the third adhesive layer 130 are damaged.
  • the first release film 141 and the second release film 142 are temporary protective layers, and the first adhesive layer 110, the second adhesive layer 120, and the third adhesive layer 130 are used layers.
  • the optical adhesive 100 it is necessary to sequentially remove the first release film 141 and the second release film 142 according to the attaching method, and constitute the first adhesive layer 110, the second adhesive layer 120, and the third adhesive layer 130.
  • the multilayer structure is attached between two parts to be attached.
  • At least one embodiment of the present disclosure further provides a display device, which includes a display panel and a cover layer disposed in a stacked manner, and an adhesive film is provided between the display panel and the cover layer, and the adhesive film includes any one of the embodiments of the present disclosure.
  • a side of the first adhesive layer of the optical adhesive remote from the second adhesive layer is subjected to compressive stress when the display device is bent.
  • the optical adhesive in the display device not only has strong adhesive ability, but also can reduce the bending stress of the components to which it is attached, can suppress the generation of air bubbles, and avoid problems such as wrinkles, fractures, and separation of film layers.
  • FIG. 3 is a schematic diagram of a layer structure of a display device provided by at least one embodiment of the present disclosure.
  • the display device 200 includes a display panel 210 and a cover layer 220 which are arranged in a stack.
  • An adhesive film 300 is disposed between the display panel 210 and the cover layer 220.
  • the adhesive film 300 is the optical adhesive 100 according to any embodiment of the present disclosure.
  • the optical adhesive 100 is used to bond the display panel 210 and the cover layer 220 together.
  • the display device 200 may be bent or folded.
  • the side of the first adhesive layer 110 of the optical adhesive 100 far from the second adhesive layer 120 is subjected to compressive stress, that is, the first adhesive layer 110 and the display panel 210 or the cover layer 220.
  • the contact side is subjected to compressive stress.
  • the optical adhesive 100 in the display device 200 not only has strong bonding ability, but also can reduce the bending stress of the components (such as the display panel 210 or the cover layer 220) to which it is attached, which can suppress the generation of air bubbles and avoid wrinkles. , Fracture, separation and other membrane failure issues.
  • the bonding direction of the optical adhesive 100 is not limited.
  • the first adhesive layer 110 in the optical adhesive 100 may be in contact with the display panel 210 or may be in contact with the cover layer 220.
  • the third adhesive layer 130 in the optical adhesive 100 may be in contact with the cover layer 220 or in contact with the display panel 210.
  • the bonding direction of the optical adhesive 100 may be determined according to the bending or folding direction of the display device 200, so that the first adhesive layer 110 is subjected to a compressive stress when the display device 200 is bent or folded.
  • the display panel 210 may be a flexible organic light emitting diode (Organic Light Emitting Diode, OLED) display panel.
  • the cover layer 220 may be a flexible protective film, such as a polyimide (PI) film.
  • PI polyimide
  • the display device 200 may further include more components and structures. These components and structures should be understood by those of ordinary skill in the art, and will not be repeated here. It should be taken as a limitation to the embodiments of the present disclosure.
  • FIG. 4 is a schematic diagram of a layer structure of another display device in a bent state according to at least one embodiment of the present disclosure.
  • the display device 200 in addition to the display panel 210 and the cover layer 220, the display device 200 further includes a polarizer 230 and a touch structure layer 240.
  • the polarizer 230 is sandwiched between the display panel 210 and the touch structure layer 240, the touch structure layer 240 is sandwiched between the polarizer 230 and the cover layer 220, and the polarizer is between the display panel 210 and the polarizer 230
  • An adhesive film 300 is provided between 230 and the touch structure layer 240 and between the touch structure layer 240 and the cover layer 220.
  • the adhesive film 300 is the optical adhesive 100 according to any embodiment of the present disclosure.
  • the display device 200 may further include other components such as a middle frame, which is not limited in the embodiments of the present disclosure.
  • FIG. 4 illustrates a bent state of the display device 200, and each side of each film layer is subjected to one of compressive stress or tensile stress, and accordingly, shear deformation occurs.
  • FIG. 5 is a simulation diagram of the strains of the film layers of the display device shown in FIG. 4 in a bent state. Referring to FIGS. 4 and 5, for example, the strain on the outside of the cover layer 220 (the side not in contact with the first adhesive film 301) is a positive value, and thus the outside of the cover layer 220 is subjected to tensile stress.
  • the strain on the inner side of the cover layer 220 (the side that is in contact with the first adhesive film 301) is negative, so the inner side of the cover layer 220 is subjected to compressive stress.
  • the strain on the side where the first adhesive film 301 is in contact with the cover layer 220 is negative, so it is subject to compressive stress; the strain on the side where the first adhesive film 301 is in contact with the touch structure layer 240 is positive, As a result, tensile stress is applied.
  • the analysis methods of the stresses of other film layers are similar, and will not be repeated here.
  • the first adhesive film 301 is the optical adhesive 100.
  • the first adhesive layer 110 and the cover layer 220 in the optical adhesive 100 are adhered to each other, so that the optical adhesive
  • the third adhesive layer 130 in 100 is adhered to the touch structure layer 240, so that the first adhesive layer 110 receives a compressive stress when the touch device 200 is bent.
  • the second adhesive film 302 and the third adhesive film 303 are also the optical adhesive 100, and the bonding direction is determined according to the strain when bonding, so that the first adhesive layer 110 can withstand pressure when the touch device 200 is bent. stress.
  • the first adhesive layer 110 in the second adhesive film 302 (optical adhesive 100) and the touch-control structure layer 240 can be laminated to make the first adhesive layer 110 in the third adhesive film 303 (optical adhesive 100). It is adhered to the polarizer 230, so that the first adhesive layer 110 is subjected to compressive stress.
  • the cover layer 220 is located outside the display panel 210, When the display panel 210 and the cover layer 220 of the display device 200 shown in FIG.
  • the first adhesive layer 110 and the cover layer 220 in the adhesive film 300 may be bonded to each other to make the adhesive
  • the third adhesive layer 130 in the adhesive film 300 is adhered to the display panel 210, so that the first adhesive layer 110 is subjected to compressive stress.
  • the optical adhesive 100 Since the optical adhesive 100 has the largest storage modulus of the first adhesive layer 110, it can withstand a large compressive stress, thereby effectively suppressing the generation of bubbles caused by bending or high temperature, and avoiding the occurrence of wrinkles.
  • the first adhesive layer 110 and the third adhesive layer 130 each have a large storage modulus, so that they have high adhesion and strong bonding ability, and can better interact with the display panel 210, the cover layer 220, the polarizer 230, and the touch panel. Components such as the control structure layer 240 are bonded.
  • the storage modulus of the second adhesive layer 120 is the smallest, which can allow large shear slip and shear strain between the film layers, so that the bending stress between the respective film layers can be partially resolved. Coupling can effectively suppress the generation of air bubbles and avoid the problems of film failure such as wrinkles, fractures and separation.
  • the display device 200 is configured to bend with a radius of curvature R, for example, 1 mm ⁇ R ⁇ 6 mm. Within this range, the display device 200 has good bending characteristics without wrinkles and breaks. , Separation and other membrane failure issues.
  • At least one embodiment of the present disclosure also provides a method for manufacturing an optical adhesive.
  • the optical adhesive manufactured by the manufacturing method not only has strong bonding ability, but also can reduce the bending stress of the components to which it is attached, and can suppress the bubbles. It can avoid the problems of film failure such as wrinkle, fracture and separation.
  • FIG. 6 is a schematic flowchart of a method for manufacturing an optical adhesive provided by at least one embodiment of the present disclosure.
  • the manufacturing method of the optical glue includes the following steps:
  • Step S410 apply the first mixture to the first release film 141, and cure the first mixture to form a first adhesive layer 110;
  • Step S420 applying the second mixture to the first mixture, and curing the second mixture to form a second adhesive layer 120;
  • Step S430 applying the third mixture to the second mixture, and curing the third mixture to form a third adhesive layer 130.
  • the storage modulus of the first adhesive layer 110 is greater than the storage modulus of the third adhesive layer 130, and the storage modulus of the first adhesive layer 110 and the storage modulus of the third adhesive layer 130 are both greater than the second The storage modulus of the adhesive layer 120.
  • the method for manufacturing an optical adhesive further includes: providing a second release film 142 and covering the second release film 142 to a side of the third adhesive layer 130 away from the second adhesive layer 120.
  • first adhesive layer 110, the second adhesive layer 120, and the third adhesive layer 130 may be formed in the same curing process, or may be formed in curing processes independent of each other, which is not limited in the embodiments of the present disclosure.
  • a first nozzle 501 is first applied to a first release film 141 (for example, a heavy release film, the material is polyethylene terephthalate, and the thickness is 75 ⁇ m).
  • the first mixture is clothed, then the second mixture is coated on the first mixture using the second nozzle 502, and then the third mixture is coated on the second mixture using the third nozzle 503.
  • the three-layer mixture is irradiated with ultraviolet (Ultraviolet Rays, UV) curing method using an ultraviolet light source 510 (for example, a low-pressure mercury lamp, brand: BL Lamp, Sankyo Co., Ltd.)
  • UV Ultraviolet Rays
  • the time is, for example, 6 minutes, so that the three-layer mixture forms the first adhesive layer 110, the second adhesive layer 120, and the third adhesive layer 130 in the same curing process, respectively.
  • the first roller 521 is rotated clockwise to drive the first release film 141 and the adhesive layer thereon, and the second roller 522 is rotated counterclockwise to drive the second release film 142 (for example, a light release film )
  • the third roller 523 is rotated counterclockwise to cover the second release film 142 to the side of the third adhesive layer 130 away from the second adhesive layer 120, and make the first release film 141 and the second release film
  • the laminated structure formed by the mold film 142 and the first to third adhesive layers 110-130 forms a reel at the winding end A.
  • the ultraviolet light source 510 may be any suitable light source such as a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a chemical lamp, a black light lamp, and the embodiment of the present disclosure is not limited thereto.
  • the irradiation energy of the ultraviolet light source 510 can be set according to actual needs, for example, according to the components of the first to third mixtures, the response rate to be achieved, and other factors, and can be, for example, 500 mj / cm 2 to 3000 mj / cm 2 .
  • the irradiation time of the ultraviolet light source 510 can also be set according to actual needs, which is not limited in the embodiments of the present disclosure.
  • the curing process is not limited to UV curing, and any applicable curing method such as thermal curing may be adopted as long as the purpose of curing can be achieved.
  • the process parameters such as irradiation energy, irradiation time, etc.
  • the proportion of the initiator is different, so that the first mixture, the second mixture, and the third mixture have different reaction rates in the same curing process, so that the first adhesive layer 110, the second adhesive layer 120, and the third adhesive layer are formed.
  • the storage modulus of 130 meets the requirements, that is, the storage modulus of the first adhesive layer 110 is greater than the storage modulus of the third adhesive layer 130, and the storage modulus of the first adhesive layer 110 and that of the third adhesive layer 130 are The storage modulus is greater than the storage modulus of the second adhesive layer 120.
  • the process of the optical adhesive 100 is not limited to the manner described above, and may also be other manners.
  • a first mixture is applied on the first release film 141 using a first nozzle 501, and then the first mixture is irradiated with an ultraviolet light source 510 to cure the first mixture to form First adhesive layer 110.
  • the second mixture is coated on the first mixture (the first mixture has been cured into the first adhesive layer 110) by using the second nozzle 502, and then the second mixture is irradiated with the ultraviolet light source 510 to cure the second mixture to form ⁇ ⁇ 120 ⁇ The second adhesive layer 120.
  • the third mixture is applied to the second mixture (the second mixture has been cured into the second adhesive layer 120) by using the third nozzle 503, and then the third mixture is irradiated with the ultraviolet light source 510 to cure the third mixture to form Third adhesive layer 130.
  • the first roller 521 is rotated clockwise to drive the first release film 141 and the adhesive layer thereon, and the second roller 522 is rotated counterclockwise to drive the second release film 142 to move the third roller.
  • the first to third mixtures can use mixtures of the same ingredients and proportions by adjusting the process parameters of each curing process (such as irradiation Energy, irradiation time, etc.), so that the reaction rates of the first to third mixtures to be coated are different, so that the storage modulus of each formed glue layer meets the requirements, that is, the storage modulus of the first glue layer 110 is greater than
  • the storage modulus of the third adhesive layer 130, and the storage modulus of the first adhesive layer 110 and the storage modulus of the third adhesive layer 130 are both greater than the storage modulus of the second adhesive layer 120.
  • the embodiments of the present disclosure are not limited to this.
  • the process parameters of the process can also be adjusted simultaneously with the components and ratios of the first to third mixtures and the process parameters of each curing process, which can be flexibly set according to actual needs.
  • each of the first, second, and third mixtures includes a monomer mixture, an initiator, and a crosslinking agent.
  • the first mixture, the second mixture, and the third mixture include the same monomer mixture, initiator, and cross-linking agent, but the content of each component is adjusted as needed; for example, the first mixture, the second mixture, and the third mixture
  • the mixture includes at least one different monomer mixture, an initiator, and a crosslinking agent.
  • the monomer mixture may include a monomer for forming a hydroxyl group-containing (meth) acrylic copolymer, such as 2-ethylhexyl acrylate (EHA), 4-hydroxybutyl acrylate (HBA), or acrylic acid. 2-hydroxyethyl ester (HEA) and the like.
  • EHA 2-ethylhexyl acrylate
  • HBA 4-hydroxybutyl acrylate
  • the hydroxyl group-containing acrylic copolymer can form a matrix of an optical glue and can provide adhesion.
  • the monomer (or resin) may be an acrylic resin, a polyurethane resin, an epoxy polyester resin, a silicon resin, a polyisoprene, a polycarbonate resin, a poly
  • the imide resin and the cycloolefin polymer resin may be, for example, a (meth) acrylic resin. Because the adhesive material has different adhesive performance to different interfaces, the first mixture used to form the first adhesive layer 110 and the third mixture used to form the third adhesive layer 130 may change the resin type and the proportion according to different interfaces.
  • the monomer mixture may include a hydroxy group-containing acrylate and a comonomer, where the "comonomer" is different from a hydroxy group-containing acrylate.
  • the hydroxy group-containing acrylate may include a (meth) acrylate containing a C 1 to C 20 alkyl group having at least one hydroxy group, a C 5 to C 20 cycloalkyl group having at least one hydroxy group At least one of a (meth) acrylate of a group and a (meth) acrylate containing a C 6 to C 20 aryl group having at least one hydroxyl group, and the embodiments of the present disclosure are not limited thereto.
  • the (meth) acrylate containing a hydroxyl group may include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (methyl At least one of 2-hydroxybutyl acrylate and 6-hydroxyhexyl (meth) acrylate, which is not limited in the examples of the present disclosure.
  • a (meth) acrylic monomer including a C 1 to C 5 alkyl group having a hydroxyl group may further improve the adhesiveness of the optical adhesive.
  • the hydroxyl group-containing (meth) acrylic monomer may be about 5 wt% to about 40 wt% by weight. Within this range, the optical adhesive has a lower haze and may exhibit good adhesion. strength.
  • the comonomer may include an alkyl (meth) acrylate monomer, an ethylene oxide-containing monomer, a propylene oxide-containing monomer, an amine group-containing monomer, an amide group-containing monomer, an alkane-containing monomer At least one of an oxy group-containing monomer, a phosphate group-containing monomer, a sulfonic acid group-containing monomer, a phenyl group-containing monomer, and a silane group-containing monomer.
  • the embodiment does not limit this.
  • the initiator may cure (or partially polymerize) the monomer mixture to form a (meth) acrylic copolymer, or may be used to cure a viscous liquid into a film.
  • the initiator may be a photopolymerization initiator or a thermal polymerization initiator, and may also be another type of initiator, which may depend on the curing method used.
  • the photopolymerization initiator may be commercially available Irgacure 651 (ingredient: 2,2-dimethoxy-2-phenylacetophenone, brand: BASF), or it may be commercially available Irgacure 184 (ingredient: 1 -Hydroxycyclohexyl phenone, brand: BASF).
  • cross-linking agents can improve the heat resistance and strength of optical adhesives, can generate chemical bonds between linear molecules, interconnect linear molecules to form a network structure, and thereby improve the performance of optical adhesives.
  • cross-linking agent hexamethylene glycol diacrylate can be used.
  • the embodiments of the present disclosure are not limited thereto, and the cross-linking agent may also adopt other applicable materials.
  • each of the first mixture, the second mixture, and the third mixture further includes organic nanoparticles.
  • the storage modulus of the optical glue decreases.
  • adding organic nanoparticles to the mixture can keep the storage modulus of the optical gel as stable as possible, and when the temperature increases, the storage modulus is not reduced or the change is small, so Improve the performance of optical adhesives at high temperatures.
  • the material of the organic nanoparticles can be polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polyisopropyl methacrylate, polymethacrylate At least one of butyl ester and polycyclohexyl methacrylate.
  • polymethyl methacrylate is used as the material of the organic nanoparticles, the storage modulus of the optical glue is better maintained.
  • the embodiments of the present disclosure are not limited thereto, and the organic nanoparticles may adopt any applicable organic material.
  • the method for preparing the first mixture, the second mixture, and the third mixture may adopt a conventional method for preparing a mixture, for example, mechanical stirring mixing, ultrasonic mixing, or the like may be adopted.
  • a monomer mixture containing 65% by weight of 2-ethylhexyl acrylate and 35% by weight of 4-hydroxybutyl acrylate in a glass container, 4 parts by weight of organic
  • the nanoparticles and 0.005 parts by weight of a photopolymerization initiator were used to prepare a mixture.
  • the mixture was irradiated with UV light from a low-pressure mercury lamp to partially polymerize the mixture, thereby obtaining a (meth) acrylic copolymer (i.e., a prepolymer) containing a hydroxyl group, A mixture of organic and organic nanoparticles and has a viscosity of about 2000 cPs.
  • a photopolymerization initiator is added to the above mixture in an amount of 5 parts by weight relative to 100 parts by weight of the monomer mixture, thereby obtaining a desired mixture (i.e., a first mixture, a second mixture, or a third mixture).
  • the above mixture can be cured to form the first glue layer 110, the second glue layer 120, or the third glue layer 130. Only the process parameters of the curing process need to be adjusted to control the reaction rate of the mixture, so that the required storage modulus can be achieved. .
  • the method for preparing a mixture is not limited to the above-mentioned manner, and the ratio of various ingredients is not limited to the above-mentioned ratio. The method for preparing a mixture and the ratio of various ingredients are common techniques in the art. Personnel should understand that it will not be repeated here and should not be used as a limitation on the embodiments of the present disclosure.
  • the monomer (or resin), the initiator, the cross-linking agent, and the organic nanoparticles are all commercially available products, and conventional materials may be used.
  • the preparation process used can be conventional coating, curing and other processes.
  • For a method of adjusting the storage modulus of the first adhesive layer 110, the second adhesive layer 120, and the third adhesive layer 130 for example, making the initiator mixture ratios of the first mixture, the second mixture, and the third mixture different, or changing
  • the parameters of the curing process make the reaction rates of the first mixture, the second mixture, and the third mixture different.
  • the first mixture, the second mixture, and the third mixture may include more or less ingredients, and the proportion of each component may be determined according to actual needs, and the ingredients of the first mixture, the second mixture, and the third mixture may be the same It may also be different, and the embodiments of the present disclosure are not limited thereto.

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Abstract

一种光学胶（100）及其制造方法、显示装置（200），光学胶（100）包括依次层叠的第一胶层（110）、第二胶层（120）和第三胶层（130），第一胶层（110）的储能模量大于第三胶层（130）的储能模量，且第一胶层（110）的储能模量和第三胶层（130）的储能模量均大于第二胶层（120）的储能模量。光学胶（100）既具有较强的胶合能力，又可以减小与之贴合的部件的弯曲应力，能够抑制气泡的产生，避免出现褶皱、断裂、分离等膜层失效的问题。

Description

光学胶及其制造方法、显示装置
本申请要求于2018年8月29日递交的中国专利申请第201810992205.0号的优先权，该中国专利申请的全文以引入的方式并入以作为本申请的一部分。
技术领域
本公开的实施例涉及一种光学胶及其制造方法、显示装置。
背景技术
随着显示技术的发展，显示装置逐渐应用到诸多领域，成为了应用最为广泛的电子设备之一。显示装置通常包括显示面板，还可以包括触控结构(例如触摸屏)、偏光片、保护结构(例如覆盖层)等部件。上述各个部件例如通过光学胶而粘结为一体。光学胶是一种用于粘结透明光学元件的特种粘胶剂，具有无色透明、光透过率高、粘结强度良好等特点。光学胶可以粘结显示装置中的各个部件，在实现粘结功能的同时，不会影响正常显示，是显示装置中重要的原材料之一。
发明内容
本公开至少一个实施例提供一种光学胶，包括依次层叠的第一胶层、第二胶层和第三胶层，其中，所述第一胶层的储能模量大于所述第三胶层的储能模量，且所述第一胶层的储能模量和所述第三胶层的储能模量均大于所述第二胶层的储能模量。
例如，在本公开一实施例提供的光学胶中，所述第一胶层的储能模量为50KPa-200KPa。
例如，在本公开一实施例提供的光学胶中，所述第二胶层的储能模量为15KPa-80KPa。
例如，在本公开一实施例提供的光学胶中，所述第三胶层的储能模量为30KPa-100KPa。
例如，在本公开一实施例提供的光学胶中，所述光学胶的玻璃化转化温 度小于-30℃。
例如，在本公开一实施例提供的光学胶中，所述第一胶层的厚度为2μm-30μm，所述第二胶层的厚度为5μm-100μm，所述第三胶层的厚度为2μm-100μm。
例如，在本公开一实施例提供的光学胶还包括：第一离型膜，设置在所述第一胶层远离所述第二胶层的一侧；第二离型膜，设置在所述第三胶层远离所述第二胶层的一侧。
例如，在本公开一实施例提供的光学胶中，所述第一胶层、所述第二胶层和所述第三胶层的透过率均大于93％，所述第一胶层、所述第二胶层和所述第三胶层的雾度均小于1％。
本公开至少一个实施例还提供一种显示装置，包括层叠设置的显示面板和覆盖层，其中，所述显示面板与所述覆盖层之间设置有粘合膜，所述粘合膜包括本公开任一实施例所述的光学胶，所述光学胶的所述第一胶层远离所述第二胶层的一侧在所述显示装置被弯曲时承受压应力。
例如，在本公开一实施例提供的显示装置中，在所述显示装置被弯曲时，所述覆盖层位于所述显示面板的外侧，所述第一胶层与所述覆盖层接触，所述第三胶层与所述显示面板接触。
例如，在本公开一实施例提供的显示装置中，所述显示面板为柔性有机发光二极管显示面板。
例如，在本公开一实施例提供的显示装置还包括偏光片，其中，所述偏光片设置在所述显示面板与所述覆盖层之间，且所述显示面板与所述偏光片之间、所述偏光片与所述覆盖层之间均设置有所述粘合膜。
例如，在本公开一实施例提供的显示装置还包括触控结构层，其中，所述触控结构层夹置在所述偏光片与所述覆盖层之间，且所述偏光片与所述触控结构层之间、所述触控结构层与所述覆盖层之间均设置有所述粘合膜。
例如，在本公开一实施例提供的显示装置中，所述显示装置配置为以1mm-6mm的曲率半径进行弯曲。
本公开至少一个实施例还提供一种光学胶的制造方法，包括：将第一混合物涂覆至第一离型膜上，将所述第一混合物固化形成第一胶层；将第二混合物涂覆至所述第一混合物上，将所述第二混合物固化形成第二胶层；将第三混合物涂覆至所述第二混合物上，将所述第三混合物固化形成第三胶层； 其中，所述第一胶层的储能模量大于所述第三胶层的储能模量，且所述第一胶层的储能模量和所述第三胶层的储能模量均大于所述第二胶层的储能模量。
例如，在本公开一实施例提供的光学胶的制造方法中，所述第一胶层、所述第二胶层和所述第三胶层在同一固化工艺中形成，或者在彼此独立的固化工艺中形成。
例如，在本公开一实施例提供的光学胶的制造方法还包括：提供第二离型膜，并将所述第二离型膜覆盖至所述第三胶层远离所述第二胶层的一侧。
例如，在本公开一实施例提供的光学胶的制造方法中，所述第一混合物、所述第二混合物和所述第三混合物各自均包括单体混合物、引发剂和交联剂。
例如，在本公开一实施例提供的光学胶的制造方法中，所述第一混合物、所述第二混合物和所述第三混合物各自还包括有机纳米颗粒。
例如，在本公开一实施例提供的光学胶的制造方法中，所述第一混合物、所述第二混合物和所述第三混合物的引发剂配比量不同，以使所述第一胶层的储能模量大于所述第三胶层的储能模量，且所述第一胶层的储能模量和所述第三胶层的储能模量均大于所述第二胶层的储能模量。
例如，在本公开一实施例提供的光学胶的制造方法中，在分别形成所述第一胶层、所述第二胶层和所述第三胶层的固化工艺中，所述第一混合物、所述第二混合物和所述第三混合物的反应率不同，以使所述第一胶层的储能模量大于所述第三胶层的储能模量，且所述第一胶层的储能模量和所述第三胶层的储能模量均大于所述第二胶层的储能模量。
附图说明
为了更清楚地说明本公开实施例的技术方案，下面将对实施例的附图作简单地介绍，显而易见地，下面描述中的附图仅仅涉及本公开的一些实施例，而非对本公开的限制。
图1为本公开至少一个实施例提供的一种光学胶的层结构示意图；
图2为本公开至少一个实施例提供的另一种光学胶的层结构示意图；
图3为本公开至少一个实施例提供的一种显示装置的层结构示意图；
图4为本公开至少一个实施例提供的另一种显示装置在弯曲状态下的层结构示意图；
图5为图4所示的显示装置在弯曲状态下各个膜层的应变的仿真示意图；
图6为本公开至少一个实施例提供的一种光学胶的制造方法的流程示意图；以及
图7为本公开至少一个实施例提供的一种光学胶的工艺制程示意图。
具体实施方式
为使本公开实施例的目的、技术方案和优点更加清楚，下面将结合本公开实施例的附图，对本公开实施例的技术方案进行清楚、完整地描述。显然，所描述的实施例是本公开的一部分实施例，而不是全部的实施例。基于所描述的本公开的实施例，本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例，都属于本公开保护的范围。
除非另外定义，本公开使用的技术术语或者科学术语应当为本公开所属领域内具有一般技能的人士所理解的通常意义。本公开中使用的“第一”、“第二”以及类似的词语并不表示任何顺序、数量或者重要性，而只是用来区分不同的组成部分。同样，“一个”、“一”或者“该”等类似词语也不表示数量限制，而是表示存在至少一个。“包括”或者“包含”等类似的词语意指出现该词前面的元件或者物件涵盖出现在该词后面列举的元件或者物件及其等同，而不排除其他元件或者物件。“连接”或者“相连”等类似的词语并非限定于物理的或者机械的连接，而是可以包括电性的连接，不管是直接的还是间接的。“上”、“下”、“左”、“右”等仅用于表示相对位置关系，当被描述对象的绝对位置改变后，则该相对位置关系也可能相应地改变。
基于智能手机、可穿戴智能设备、虚拟现实、增强现实等领域对柔性显示的需求，柔性显示技术逐渐成为下一代核心显示技术。柔性显示装置可以弯曲或折叠，适用于多种应用场景，有效提升了用户的使用体验。
柔性显示装置通常包括柔性显示面板和多个外部构件，这些部件通过光学胶彼此粘接。在柔性显示装置弯曲或折叠的过程中，柔性显示面板及外部构件的应变由压应力或张应力中的任意一种应力产生。由于应力的作用，柔性显示装置中的各个部件可能会出现褶皱、断裂、分离等膜层失效等问题。因此，在柔性显示装置中，需要设置应力控制件(即中性层)，从而使各个部件在弯折过程中具有较小的形变量。例如，应力控制件通常为光学胶，而常 规的光学胶的应力控制作用有限，难以满足应用需求。
本公开至少一实施例提供一种光学胶及其制造方法、显示装置，该光学胶既具有较强的胶合能力，又可以减小与之贴合的部件的弯曲应力，能够抑制气泡的产生，避免出现褶皱、断裂、分离等膜层失效的问题。
下面，将参考附图详细地说明本公开的实施例。应当注意的是，不同的附图中相同的附图标记将用于指代已描述的相同的元件。
本公开至少一实施例提供一种光学胶，包括依次层叠的第一胶层、第二胶层和第三胶层。第一胶层的储能模量大于第三胶层的储能模量，且第一胶层的储能模量和第三胶层的储能模量均大于第二胶层的储能模量。
图1为本公开至少一个实施例提供的一种光学胶的层结构示意图。参考图1，该光学胶100包括依次层叠的第一胶层110、第二胶层120和第三胶层130。例如，各个胶层的储能模量不同。例如，第一胶层110的储能模量大于第三胶层130的储能模量，且第一胶层110的储能模量和第三胶层130的储能模量均大于第二胶层120的储能模量。也即是，在该三个胶层中，第一胶层110的储能模量最大，第二胶层120的储能模量最小，第三胶层130的储能模量介于第一胶层110的储能模量和第二胶层120的储能模量之间。例如，各个胶层的储能模量与硬度正相关，即储能模量越大，硬度越大。储能模量表示材料存储弹性变形能量的能力，是材料变形后回弹的指标。
例如，在至少一个示例中，第一胶层110的储能模量为50KPa-200KPa，例如可以进一步为50KPa-100KPa。例如，第二胶层120的储能模量为15KPa-80KPa，例如可以进一步为15KPa-50KPa。例如，第三胶层130的储能模量为30KPa-100KPa。上述各个胶层的储能模量均在1Hz的频率下测得。
例如，光学胶100的玻璃化转化温度小于-30℃，例如还可以进一步小于-40℃，以使得采用该光学胶100的显示装置在低温下具有更好的折叠性能。例如，该光学胶100的使用温度可以为-30℃至70℃，例如还可以进一步为-40℃至85℃。
例如，在至少一个示例中，第一胶层110的厚度为2μm-30μm，例如还可以进一步为2μm-25μm或2μm-10μm。第二胶层120的厚度为5μm-100μm，例如还可以进一步为5μm-50μm。第三胶层130的厚度为2μm-100μm，例如还可以进一步为5μm-25μm。例如，第一胶层110和第三胶层130的厚度可以相同，也可以不同，这可以根据第一胶层110和第三胶层130各自接触的 界面、位于叠层结构中的位置等因素而定。
例如，第一胶层110、第二胶层120和第三胶层130的光透过率均大于93％，第一胶层110、第二胶层120和第三胶层130的雾度均小于1％。
在使用时，光学胶100贴合在另行设置的其他部件之间。通过选择合适的贴合方向，在与光学胶100贴合的部件弯曲或折叠时，使第一胶层110远离第二胶层120的一侧承受压应力(也即，第一胶层110与其他部件接触的一侧承受压应力)。由于在该三个胶层中，第一胶层110的储能模量最大，因此第一胶层110可以承受较大的压应力，从而能够有效抑制弯折或高温导致的气泡的产生，并且可以避免产生褶皱。第一胶层110和第三胶层130的储能模量均较大，具有高粘性，具有较强的胶合能力，可以更好地与其他部件贴合。在该三个胶层中，第二胶层120的储能模量最小，可以允许膜层之间有较大的剪切滑移和剪切应变，从而可以减小与之贴合的部件的弯曲应力，可以有效抑制气泡的产生，避免出现褶皱、断裂、分离等膜层失效的问题。
需要说明的是，本公开的实施例中，光学胶100不限于第一胶层110、第二胶层120和第三胶层130构成的三层结构，还可以为任意的多层结构，例如，4层、5层等，例如使得多层结构中储能模量最大的胶层与另行设置的其他部件接触的一侧在弯曲时承受压应力，且多层结构中与其他部件接触的胶层的储能模量大于多层结构中不与其他部件接触的胶层的储能模量。例如，可以在第一胶层110和第二胶层120之间添加第四胶层，该第四胶层的储能模量介于第一胶层110和第二胶层120的储能模量之间，且可以大于或小于第三胶层130的储能模量；在此基础上，还可以在第二胶层120和第三胶层130之间添加第五胶层，该第五胶层的储能模量介于第二胶层120和第三胶层130的储能模量之间，且可以大于或小于第四胶层的储能模量。
图2为本公开至少一个实施例提供的另一种光学胶的层结构示意图。参考图2，除了还进一步包括第一离型膜141和第二离型膜142外，该实施例的光学胶100与图1所示的光学胶100基本相同。在该实施例中，第一离型膜141设置在第一胶层110远离第二胶层120的一侧；第二离型膜142设置在第三胶层130远离第二胶层120的一侧。
第一离型膜141覆盖第一胶层110将与其他部件贴合的表面，第二离型膜142覆盖第三胶层130将与其他部件贴合的表面，将与第一胶层110贴合的其他部件和将与第三胶层130贴合的其他部件不同。第一离型膜141和第 二离型膜142可以起到保护作用，以防止第一胶层110、第二胶层120和第三胶层130在与其他部件贴合之前损坏，且便于收卷、储存和运输。例如，第一离型膜141和第二离型膜142可以为PET(Polyethylene Terephthalate)离型膜，且第一离型膜141为重离型膜，第二离型膜142为轻离型膜。例如，第一离型膜141和第二离型膜142各自的离型力、厚度等参数可以根据实际需求而定，以具有较好的剥离效果，且在剥离时不会使第一胶层110、第二胶层120和第三胶层130受到损伤。
例如，第一离型膜141和第二离型膜142为临时保护层，第一胶层110、第二胶层120和第三胶层130为使用层。在使用该光学胶100时，需要根据贴附方式依次去除第一离型膜141和第二离型膜142，并将第一胶层110、第二胶层120和第三胶层130构成的多层结构贴合至两个待贴合部件之间。
本公开至少一实施例还提供一种显示装置，该显示装置包括层叠设置的显示面板和覆盖层，显示面板与覆盖层之间设置有粘合膜，该粘合膜包括本公开任一实施例所述的光学胶，该光学胶的第一胶层远离第二胶层的一侧在该显示装置被弯曲时承受压应力。该显示装置中的光学胶既具有较强的胶合能力，又可以减小与之贴合的部件的弯曲应力，能够抑制气泡的产生，避免出现褶皱、断裂、分离等膜层失效的问题。
图3为本公开至少一个实施例提供的一种显示装置的层结构示意图。参考图3，该显示装置200包括层叠设置的显示面板210和覆盖层220。显示面板210与覆盖层220之间设置有粘合膜300，粘合膜300为本公开任一实施例所述的光学胶100。
例如，光学胶100用于将显示面板210和覆盖层220粘结为一体。例如，该显示装置200可以弯曲或折叠。在显示装置200被弯曲或折叠的过程中，光学胶100的第一胶层110远离第二胶层120的一侧承受压应力，也即，第一胶层110与显示面板210或覆盖层220接触的一侧承受压应力。该显示装置200中的光学胶100既具有较强的胶合能力，又可以减小与之贴合的部件(例如显示面板210或覆盖层220)的弯曲应力，能够抑制气泡的产生，避免出现褶皱、断裂、分离等膜层失效的问题。该光学胶100的相关描述可以参考前述内容，此处不再赘述。
例如，光学胶100的贴合方向不受限制，光学胶100中的第一胶层110可以与显示面板210接触，也可以与覆盖层220接触。相应地，光学胶100 中的第三胶层130可以与覆盖层220接触，也可以与显示面板210接触。例如，可以根据显示装置200的弯曲或折叠方向确定光学胶100的贴合方向，以在显示装置200被弯曲或折叠时，使第一胶层110承受压应力。
例如，显示面板210可以为柔性有机发光二极管(Organic Light Emitting Diode,OLED)显示面板。例如，覆盖层220可以为柔性保护膜，例如聚酰亚胺(Polyimide,PI)薄膜。需要说明的是，本公开的实施例中，显示装置200还可以包括更多的部件和结构，这些部件和结构均为本领域的普通技术人员应该理解具有的，在此不做赘述，也不应作为对本公开实施例的限制。
图4为本公开至少一个实施例提供的另一种显示装置在弯曲状态下的层结构示意图。参考图4，除了包括显示面板210和覆盖层220外，该显示装置200还进一步包括偏光片230和触控结构层240。偏光片230夹置在显示面板210与触控结构层240之间，触控结构层240夹置在偏光片230与覆盖层220之间，并且，显示面板210与偏光片230之间、偏光片230与触控结构层240之间、触控结构层240与覆盖层220之间均设置有粘合膜300。粘合膜300为本公开任一实施例所述的光学胶100。通过设置多层粘合膜300(光学胶100)，可以将显示面板210、偏光片230、触控结构层240和覆盖层220等多个部件粘结为一体。例如，该显示装置200还可以包括中框等其他部件，本公开的实施例对此不作限制。
例如，图4示出了显示装置200的弯曲状态，各个膜层的每一侧均受到压应力或张应力中的一种，因此会相应地产生剪切形变。图5为图4所示的显示装置在弯曲状态下各个膜层的应变的仿真示意图。参考图4和图5，例如，覆盖层220的外侧(不与第一粘合膜301接触的一侧)的应变为正值，因此覆盖层220的外侧受到张应力。覆盖层220的内侧(与第一粘合膜301接触的一侧)的应变为负值，因此覆盖层220的内侧受到压应力。同样地，第一粘合膜301与覆盖层220接触的一侧的应变为负值，因此受到压应力；第一粘合膜301与触控结构层240接触的一侧的应变为正值，因此受到张应力。其他各膜层所受应力的分析方式类似，此处不再赘述。
例如，第一粘合膜301为光学胶100，在对覆盖层220和触控结构层240进行粘接时，使光学胶100中的第一胶层110与覆盖层220贴合，使光学胶100中的第三胶层130与触控结构层240贴合，从而使得第一胶层110在触控装置200被弯曲时承受压应力。同样地，第二粘合膜302和第三粘合膜303 也为光学胶100，在粘接时根据应变确定贴合方向，以使第一胶层110在触控装置200被弯曲时承受压应力。例如，可以使第二粘合膜302(光学胶100)中的第一胶层110与触控结构层240贴合，使第三粘合膜303(光学胶100)中的第一胶层110与偏光片230贴合，从而使得第一胶层110承受压应力。例如，当图3所示的显示装置200在工作时需要沿着如图4所示的方向进行弯曲时，也即是，在显示装置200被弯曲时，覆盖层220位于显示面板210的外侧，在对图3所示的显示装置200的显示面板210和覆盖层220进行贴合时，可以使粘合膜300(光学胶100)中的第一胶层110与覆盖层220贴合，使粘合膜300中的第三胶层130与显示面板210贴合，从而使得第一胶层110承受压应力。
由于在光学胶100中，第一胶层110的储能模量最大，因此可以承受较大的压应力，从而能够有效抑制弯折或高温导致的气泡的产生，并且可以避免产生褶皱。第一胶层110和第三胶层130的储能模量均较大，从而具有高粘性，具有较强的胶合能力，可以更好地与显示面板210、覆盖层220、偏光片230和触控结构层240等部件贴合。在光学胶100中，第二胶层120的储能模量最小，可以允许膜层之间有较大的剪切滑移和剪切应变，从而可以使各个膜层之间的弯曲应力部分解耦，可以有效抑制气泡的产生，避免出现褶皱、断裂、分离等膜层失效的问题。
例如，如图4所示，显示装置200配置为以曲率半径R进行弯曲，例如，1mm<R<6mm，在该范围内，显示装置200具有良好的弯折特性，且不会出现褶皱、断裂、分离等膜层失效的问题。
本公开至少一实施例还提供一种光学胶的制造方法，利用该制造方法制造的光学胶既具有较强的胶合能力，又可以减小与之贴合的部件的弯曲应力，能够抑制气泡的产生，避免出现褶皱、断裂、分离等膜层失效的问题。
图6为本公开至少一个实施例提供的一种光学胶的制造方法的流程示意图。利用该光学胶的制造方法，可以制造本公开任一实施例所述的光学胶100。例如，参考图6，在至少一个示例中，该光学胶的制造方法包括以下步骤：
步骤S410：将第一混合物涂覆至第一离型膜141上，将第一混合物固化形成第一胶层110；
步骤S420：将第二混合物涂覆至第一混合物上，将第二混合物固化形成第二胶层120；
步骤S430：将第三混合物涂覆至第二混合物上，将第三混合物固化形成第三胶层130。
例如，第一胶层110的储能模量大于第三胶层130的储能模量，且第一胶层110的储能模量和第三胶层130的储能模量均大于第二胶层120的储能模量。
例如，在至少一个示例中，该光学胶的制造方法还包括：提供第二离型膜142，并将第二离型膜142覆盖至第三胶层130远离第二胶层120的一侧。
例如，第一胶层110、第二胶层120和第三胶层130可以在同一固化工艺中形成，也可以在彼此独立的固化工艺中形成，本公开的实施例对此不作限制。
在实施该光学胶的制造方法时，可以根据实际需求确定具体的工艺制程。例如，参考图7，在至少一个示例中，首先采用第一喷嘴501在第一离型膜141(例如重离型膜，材料为聚对苯二甲酸乙二醇酯，厚度为75μm)上涂布第一混合物，接着采用第二喷嘴502在第一混合物上涂布第二混合物，然后采用第三喷嘴503在第二混合物上涂布第三混合物。在三层混合物涂布完毕后，采用紫外线(Ultraviolet Rays,UV)固化的方式，使用紫外线光源510(例如低压汞灯，品牌：BL Lamp,Sankyo Co.,Ltd.)照射该三层混合物，照射时间例如为6分钟，从而使该三层混合物在同一固化工艺中分别形成第一胶层110、第二胶层120和第三胶层130。使第一辊521以顺时针方向旋转以带动第一离型膜141及其上的胶层运动，使第二辊522以逆时针方向旋转以带动第二离型膜142(例如轻离型膜)运动，使第三辊523以逆时针方向旋转以将第二离型膜142覆盖至第三胶层130远离第二胶层120的一侧，并且使得第一离型膜141、第二离型膜142及第一至第三胶层110-130形成的层叠结构在收卷端A处形成卷轴。
例如，紫外线光源510可以为低压汞灯、中压汞灯、高压汞灯、化学灯、黑光灯等任意适用的光源，本公开的实施例对此不作限制。紫外线光源510的照射能量可以根据实际需求而设置，例如根据第一至第三混合物的成分、需要达到的反应率等因素而定，例如可以为500mj/cm 2-3000mj/cm 2。紫外线光源510的照射时间也可以根据实际需求而设置，本公开的实施例对此不作限制。
需要说明的是，本公开的实施例中，固化工艺不限于UV固化，也可以 采用热固化等任意适用的固化方式，只要能达到固化的目的即可。在该示例中，由于第一至第三混合物在同一固化工艺中固化，其工艺参数(例如照射能量、照射时间等)均相同，因此可以通过使第一混合物、第二混合物和第三混合物的引发剂配比量不同，使得第一混合物、第二混合物和第三混合物在同一固化工艺中具有不同的反应率，以使形成的第一胶层110、第二胶层120和第三胶层130的储能模量达到要求，即第一胶层110的储能模量大于第三胶层130的储能模量，且第一胶层110的储能模量和第三胶层130的储能模量均大于第二胶层120的储能模量。
光学胶100的工艺制程不限于上文描述的方式，还可以为其他方式。例如，参考图7，在另一个示例中，首先，采用第一喷嘴501在第一离型膜141上涂布第一混合物，然后使用紫外线光源510照射第一混合物，以使第一混合物固化形成第一胶层110。其次，采用第二喷嘴502在第一混合物(此时第一混合物已固化为第一胶层110)上涂布第二混合物，然后使用紫外线光源510照射第二混合物，以使第二混合物固化形成第二胶层120。接着，采用第三喷嘴503在第二混合物(此时第二混合物已固化为第二胶层120)上涂布第三混合物，然后使用紫外线光源510照射第三混合物，以使第三混合物固化形成第三胶层130。使第一辊521以顺时针方向旋转以带动第一离型膜141及其上的胶层运动，使第二辊522以逆时针方向旋转以带动第二离型膜142运动，使第三辊523以逆时针方向旋转以将第二离型膜142覆盖至第三胶层130远离第二胶层120的一侧，并且使得第一离型膜141、第二离型膜142及第一至第三胶层110-130形成的层叠结构在收卷端A处形成卷轴。
在该示例中，由于第一至第三混合物分别在彼此独立的固化工艺中固化，因此第一至第三混合物可以采用相同成分和配比的混合物，通过调节各个固化工艺的工艺参数(例如照射能量、照射时间等)，使被涂覆的第一至第三混合物的反应率不同，从而使形成的各个胶层的储能模量达到要求，即第一胶层110的储能模量大于第三胶层130的储能模量，且第一胶层110的储能模量和第三胶层130的储能模量均大于第二胶层120的储能模量。当然，本公开的实施例不限于此，在该示例中，为了使各个胶层的储能模量达到要求，可以仅调节第一至第三混合物的成分和配比，也可以仅调节各个固化工艺的工艺参数，还可以同时调节第一至第三混合物的成分和配比以及各个固化工艺的工艺参数，这可以根据实际需求灵活设置。
例如，第一混合物、第二混合物和第三混合物各自均包括单体混合物、引发剂和交联剂。例如，第一混合物、第二混合物和第三混合物包括相同的单体混合物、引发剂和交联剂，但是各组分的含量根据需要调整；又例如，第一混合物、第二混合物和第三混合物包括至少之一不同的单体混合物、引发剂和交联剂。
例如，单体混合物可以包括用于形成含羟基基团的(甲基)丙烯酸类共聚物的单体，例如丙烯酸2-乙基己酯(EHA)、丙烯酸4-羟丁酯(HBA)或丙烯酸2-羟乙酯(HEA)等。含羟基基团的丙烯酸类共聚物可以形成光学胶的基体并且可以提供粘合性。当然，本公开的实施例不限于此，单体(或树脂)可以为丙烯酸类树脂、聚氨酯类树脂、环氧聚酯类树脂、硅类树脂、聚异戊二烯、聚碳酸酯树脂、聚酰亚胺树脂和环烯烃聚合物树脂中的一种或多种，例如还可以进一步为(甲基)丙烯酸类树脂。由于胶材对不同界面的粘性表现不同，用于形成第一胶层110的第一混合物和用于形成第三胶层130的第三混合物可根据接触的不同界面更改树脂类型及配比。
例如，单体混合物可以包括含羟基基团的丙烯酸酯和共聚单体，这里，“共聚单体”不同于含羟基基团的丙烯酸酯。含羟基基团的丙烯酸酯可以包括含有具有至少一个羟基基团的C 1至C 20烷基基团的(甲基)丙烯酸酯、含有具有至少一个羟基基团的C 5至C 20环烷基基团的(甲基)丙烯酸酯和含有具有至少一个羟基基团的C 6至C 20芳基基团的(甲基)丙烯酸酯中的至少一种，本公开的实施例对此不作限制。
例如，含羟基基团的(甲基)丙烯酸酯可以包括(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸4-羟丁酯、(甲基)丙烯酸2-羟丙酯、(甲基)丙烯酸2-羟丁酯和(甲基)丙烯酸6-羟己酯中的至少一种，本公开的实施例对此不作限制。
例如，包含具有羟基基团的C 1至C 5烷基基团的(甲基)丙烯酸单体可以进一步改善光学胶的粘合性。在单体混合物中，含羟基基团的(甲基)丙烯酸单体可以按重量计约5wt％至约40wt％，在此范围内，光学胶具有较低的雾度并且可以表现良好的粘结强度。
例如，共聚单体可以包括(甲基)丙烯酸烷基酯单体、含氧化乙烯的单体、含氧化丙烯的单体、含胺基团的单体、含酰胺基团的单体、含烷氧基基团的单体、含磷酸基团的单体、含磺酸基团的单体、含苯基基团的单体和含 硅烷基团的单体中的至少一种，本公开的实施例对此不作限制。
例如，引发剂可以使单体混合物固化(或部分聚合)，以形成(甲基)丙烯酸共聚物，或者可以用于将粘性液体固化成膜。引发剂可以为光聚合引发剂或热聚合引发剂，也可以为其他类型的引发剂，这可以根据采用的固化方式而定。例如，光聚合引发剂可以为市售的Irgacure 651(成分：2,2-二甲氧基-2-苯基苯乙酮，品牌：BASF)，也可以为市售的Irgacure 184(成分：1-羟基环己基苯酮，品牌：BASF)。
例如，交联剂可以改善光学胶的耐热性能和强度，可以在线型的分子之间产生化学键，使线型分子相互连在一起，形成网状结构，从而提升光学胶的性能。例如，交联剂可以采用1,6-二丙烯酸己二醇酯。当然，本公开的实施例不限于此，交联剂也可以采用其他适用的材料。
例如，在至少一个示例中，第一混合物、第二混合物和第三混合物各自还包括有机纳米颗粒。在通常情况下，随着温度的升高，光学胶的储能模量会降低。在本公开的实施例中，在混合物中加入有机纳米颗粒，可以使光学胶的储能模量尽可能保持稳定，在温度升高时，使储能模量不降低或者变化量很小，从而提高光学胶在高温下的使用性能。例如，有机纳米颗粒的材料可以采用聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯、聚甲基丙烯酸丙酯、聚甲基丙烯酸丁酯、聚甲基丙烯酸异丙酯、聚甲基丙烯酸异丁酯、聚甲基丙烯酸环已酯中的至少一种。例如，有机纳米颗粒的材料采用聚甲基丙烯酸甲酯时，对光学胶的储能模量的维持作用更好。当然，本公开的实施例不限于此，有机纳米颗粒可以采用任意适用的有机材料。
在本公开的实施例中，制备第一混合物、第二混合物和第三混合物的方法可以采用常规的制备混合物的方法，例如可以采用机械搅拌混合、超声混合等。例如，在至少一个示例中，通过在玻璃容器中充分混合100重量份的包含65wt％的丙烯酸2-乙基己酯和35wt％的丙烯酸4-羟丁酯的单体混合物、4重量份的有机纳米颗粒和0.005重量份的光聚合引发剂来制备混合物。在用氮气置换玻璃容器中溶解的氧气之后，使用低压汞灯的UV光照射混合物，使混合物部分聚合，从而得到包含羟基基团的(甲基)丙烯酸类共聚物(即预聚物)、单体和有机纳米颗粒的混合物，且具有约2000cPs的粘度。以相对于100重量份的单体混合物的5重量份的量，将光聚合引发剂添加至上述混合物中，从而得到所需要的混合物(即第一混合物、第二混合物或第三混合 物)。
例如，上述混合物可以固化形成第一胶层110、第二胶层120或第三胶层130，只需调节固化工艺的工艺参数以控制该混合物的反应率，从而可以达到需要的储能模量。需要说明的是，本公开的实施例中，制备混合物的方法不限于上述方式，各种成分的配比也不限于上述比例，制备混合物的方法和各种成分的配比为本领域的普通技术人员应该理解的，在此不做赘述，也不应作为对本公开实施例的限制。
需要说明的是，本公开的实施例中，单体(或树脂)、引发剂、交联剂和有机纳米颗粒均为市购商品，可以采用常规材料。采用的制备工艺可以为常规的涂布、固化等工艺。对于调节第一胶层110、第二胶层120和第三胶层130的储能模量的方法(例如使第一混合物、第二混合物和第三混合物的引发剂配比量不同，或者改变固化工艺的参数使第一混合物、第二混合物和第三混合物的反应率不同)，本领域的普通技术人员应该理解，在此不做赘述，也不应作为对本公开实施例的限制。第一混合物、第二混合物和第三混合物可以包括更多或更少的成分，各个成分的配比可以根据实际需求而定，并且，第一混合物、第二混合物和第三混合物的成分可以相同也可以不同，本公开的实施例对此不作限制。
有以下几点需要说明：
(1)本公开实施例附图只涉及到本公开实施例涉及到的结构，其他结构可参考通常设计。
(2)在不冲突的情况下，本公开的实施例及实施例中的特征可以相互组合以得到新的实施例。
以上所述仅是本公开的示范性实施方式，而非用于限制本公开的保护范围，本公开的保护范围由所附的权利要求确定。

Claims (21)

  1. 一种光学胶，包括依次层叠的第一胶层、第二胶层和第三胶层，其中，
    所述第一胶层的储能模量大于所述第三胶层的储能模量，且所述第一胶层的储能模量和所述第三胶层的储能模量均大于所述第二胶层的储能模量。
  2. 根据权利要求1所述的光学胶，其中，所述第一胶层的储能模量为50KPa-200KPa。
  3. 根据权利要求1或2所述的光学胶，其中，所述第二胶层的储能模量为15KPa-80KPa。
  4. 根据权利要求1-3任一所述的光学胶，其中，所述第三胶层的储能模量为30KPa-100KPa。
  5. 根据权利要求1-4任一所述的光学胶，其中，所述光学胶的玻璃化转化温度小于-30℃。
  6. 根据权利要求1-5任一所述的光学胶，其中，所述第一胶层的厚度为2μm-30μm，所述第二胶层的厚度为5μm-100μm，所述第三胶层的厚度为2μm-100μm。
  7. 根据权利要求1-6任一所述的光学胶，还包括：
    第一离型膜，设置在所述第一胶层远离所述第二胶层的一侧；
    第二离型膜，设置在所述第三胶层远离所述第二胶层的一侧。
  8. 根据权利要求1-7任一所述的光学胶，其中，所述第一胶层、所述第二胶层和所述第三胶层的透过率均大于93％，所述第一胶层、所述第二胶层和所述第三胶层的雾度均小于1％。
  9. 一种显示装置，包括层叠设置的显示面板和覆盖层，其中，
    所述显示面板与所述覆盖层之间设置有粘合膜，所述粘合膜包括根据权利要求1-8任一所述的光学胶，
    所述光学胶的所述第一胶层远离所述第二胶层的一侧在所述显示装置被弯曲时承受压应力。
  10. 根据权利要求9所述的显示装置，其中，在所述显示装置被弯曲时，所述覆盖层位于所述显示面板的外侧，
    所述第一胶层与所述覆盖层接触，所述第三胶层与所述显示面板接触。
  11. 根据权利要求9或10所述的显示装置，其中，所述显示面板为柔性 有机发光二极管显示面板。
  12. 根据权利要求9所述的显示装置，还包括偏光片，其中，
    所述偏光片设置在所述显示面板与所述覆盖层之间，且所述显示面板与所述偏光片之间、所述偏光片与所述覆盖层之间均设置有所述粘合膜。
  13. 根据权利要求12所述的显示装置，还包括触控结构层，其中，
    所述触控结构层夹置在所述偏光片与所述覆盖层之间，且所述偏光片与所述触控结构层之间、所述触控结构层与所述覆盖层之间均设置有所述粘合膜。
  14. 根据权利要求9-13任一所述的显示装置，其中，所述显示装置配置为以1mm-6mm的曲率半径进行弯曲。
  15. 一种光学胶的制造方法，包括：
    将第一混合物涂覆至第一离型膜上，将所述第一混合物固化形成第一胶层；
    将第二混合物涂覆至所述第一混合物上，将所述第二混合物固化形成第二胶层；
    将第三混合物涂覆至所述第二混合物上，将所述第三混合物固化形成第三胶层；
    其中，所述第一胶层的储能模量大于所述第三胶层的储能模量，且所述第一胶层的储能模量和所述第三胶层的储能模量均大于所述第二胶层的储能模量。
  16. 根据权利要求15所述的光学胶的制造方法，其中，所述第一胶层、所述第二胶层和所述第三胶层在同一固化工艺中形成，或者在彼此独立的固化工艺中形成。
  17. 根据权利要求15或16所述的光学胶的制造方法，还包括：
    提供第二离型膜，并将所述第二离型膜覆盖至所述第三胶层远离所述第二胶层的一侧。
  18. 根据权利要求15-17任一所述的光学胶的制造方法，其中，所述第一混合物、所述第二混合物和所述第三混合物各自均包括单体混合物、引发剂和交联剂。
  19. 根据权利要求18所述的光学胶的制造方法，其中，所述第一混合物、所述第二混合物和所述第三混合物各自还包括有机纳米颗粒。
  20. 根据权利要求18或19所述的光学胶的制造方法，其中，所述第一混合物、所述第二混合物和所述第三混合物的引发剂配比量不同，以使所述第一胶层的储能模量大于所述第三胶层的储能模量，且所述第一胶层的储能模量和所述第三胶层的储能模量均大于所述第二胶层的储能模量。
  21. 根据权利要求15-20任一所述的光学胶的制造方法，其中，在分别形成所述第一胶层、所述第二胶层和所述第三胶层的固化工艺中，所述第一混合物、所述第二混合物和所述第三混合物的反应率不同，以使所述第一胶层的储能模量大于所述第三胶层的储能模量，且所述第一胶层的储能模量和所述第三胶层的储能模量均大于所述第二胶层的储能模量。
PCT/CN2019/099661 2018-08-29 2019-08-07 光学胶及其制造方法、显示装置 WO2020042885A1 (zh)

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