WO2023245624A1 - 纳米银线光阻剂、触控结构和显示装置 - Google Patents

纳米银线光阻剂、触控结构和显示装置 Download PDF

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WO2023245624A1
WO2023245624A1 PCT/CN2022/101145 CN2022101145W WO2023245624A1 WO 2023245624 A1 WO2023245624 A1 WO 2023245624A1 CN 2022101145 W CN2022101145 W CN 2022101145W WO 2023245624 A1 WO2023245624 A1 WO 2023245624A1
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conductive
group
groups
display
layer
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PCT/CN2022/101145
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English (en)
French (fr)
Inventor
钟美弟
陈宇龙
李伟
运向军
汤俊松
戴嘉倩
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深圳市邦得凌半导体材料有限公司
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Priority to PCT/CN2022/101145 priority Critical patent/WO2023245624A1/zh
Publication of WO2023245624A1 publication Critical patent/WO2023245624A1/zh

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • 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
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means

Definitions

  • the present invention relates to the technical field of photoresist, and in particular to a nano-silver wire photoresist including nano-silver wire and dispersed resin, as well as a touch structure and a display device using the nano-silver wire photoresist.
  • the touch display screen is one of the most important components of various smart display touch terminals represented by smartphones.
  • the touch display screen is the terminal hardware that realizes human-computer interaction and multimedia information transmission.
  • touch control is an important bottleneck technology.
  • ITO the most mature touch capacitive material currently available, cannot be effectively reduced to less than 100 ohms/resistance when the touch sensor size exceeds 32 inches, causing the touch driver chip to be ineffective.
  • the touch signal is transmitted, resulting in a poor touch operation experience.
  • the touch sensor can be integrated on the surface of the cover or the surface of the display, it will not only reduce the number of structural layers of the whole machine, but also improve the optical performance.
  • An existing method uses nano-silver wire photoresist to make the touch layer.
  • the problem is that the nano-silver wire is easy to agglomerate and flocculate, causing the coatability of the nano-silver wire photoresist to fail to meet the requirements, thus causing the production
  • the transparent conductive lines are not fine enough, affecting the touch effect.
  • one of the objects of the present invention is to provide a nano-silver wire photoresist, which has good conductivity and high light transmittance, and has low viscosity and good coating properties. It has good cloth performance.
  • it can replace ITO to make various transparent electrodes with reduced resistance. It especially overcomes the shortcomings of ITO that is not resistant to bending. It has great advantages in flexible touch displays. Good performance.
  • the second object of the present invention is to provide a touch control structure and a manufacturing method thereof, through which the touch control structure can obtain a sensitive touch effect, realize bendable and flexible touch, and reduce the process flow and cost.
  • a third object of the present invention is to provide a display device containing a touch structure and a manufacturing method thereof.
  • the display device can obtain a sensitive touch effect, realize bendable and flexible touch, and reduce the manufacturing process and cost.
  • a nano-silver wire photoresist includes nano-silver wire and dispersion resin.
  • the function of the dispersion resin is to stabilize rheology and resist agglomeration and flocculation.
  • the dispersion resin is represented by formula (1):
  • Z represents H, or an acrylic copolymer containing amino group, epoxy group, alkyl group with 1 to 14 carbon atoms, cycloalkyl group or aryl substituent with 3 to 14 carbon atoms;
  • R represents C, N, CH group, Or at least one of linear alkyl groups containing 2-14 carbon atoms, aliphatic cycloalkyl groups containing 2-14 carbon atoms, aryl groups and heteroaryl groups containing 3-14 carbon atoms;
  • A is represented by formula (2):
  • W is connected to Z, the carboxyl group is connected to R, and W represents an H atom, a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, and an alkylene oxide having 2 to 6 carbon atoms. group, at least one of a substituted or unsubstituted aryl group having 3 to 14 carbon atoms and a substituted or unsubstituted heteroaryl group.
  • the dispersion resin is a terminal oligomer molecular dispersant with the above structure.
  • the terminal groups of the dispersion resin molecule are methacrylic acid and styrene copolymer, polyester copolymer, polyurethane copolymer, epoxy resin copolymer, hydroxyethyl group One or two or more of cellulose ether, hydroxypropyl methylcellulose, methyl hydroxyethyl cellulose ether or polyvinyl butyral.
  • the solid content in the dispersion is 0.1-20%, preferably 1-10%, and more preferably 2-5%.
  • Z represents selected from the group consisting of methacrylic acid, acrylic acid, benzyl acrylate, styrene, methyl methacrylate, butyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, tricyclic methacrylate [5.2 .1.02,6]Dec-8-yl ester, hydroxyethyl methacrylate, hydroxybutyl acrylate, azophenyl maleimide, maleic anhydride, 2-acrylic acid-2hydroxy-3-phenoxy Copolymers of more than one compound from the group consisting of propyl ester or pentaerythritol acrylate, and/or
  • W represents at least one of H, methyl, ethyl, hydroxyl-substituted alkyl, epoxyalkyl, phenyl, benzyl, and phenol.
  • A represents at least one of the compounds represented by the following formulas:
  • the above-mentioned dispersion resin can be obtained by the following preparation method, including the following steps:
  • acrylic compounds containing amino groups, epoxy groups, alkyl groups with 1 to 14 carbon atoms, cycloalkyl groups with 3 to 14 carbon atoms or aryl substituents are added to In the first solvent containing the chain transfer agent, under an inert atmosphere, the acrylic copolymer Z is generated through free radical solution polymerization;
  • the obtained acrylic copolymer Z and the intermediate are reacted in a second solvent in the presence of a catalyst to generate a dispersion resin.
  • the intermediate used to prepare the dispersion resin is represented by formula (3):
  • X represents halogen
  • R represents C, N, CH group, Or at least one of linear alkyl groups containing 2-14 carbon atoms, aliphatic cycloalkyl groups containing 2-14 carbon atoms, aryl groups and heteroaryl groups containing 3-14 carbon atoms;
  • A is represented by formula (2):
  • W is connected to At least one of a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group having 3 to 14 carbon atoms.
  • the wavy lines in the formula are used to indicate the connection of other groups.
  • X is Cl, Br or I
  • W represents at least one of H, methyl, ethyl, hydroxyl-substituted alkyl, epoxyalkyl, phenyl, benzyl, and phenol.
  • the intermediate is one of the compounds represented by the following formulas:
  • X represents a halogen, preferably Cl, Br or I, and more preferably Br.
  • the obtained acrylic copolymer Z and the intermediate are heated and dissolved in a second solvent in the presence of a catalyst and refluxed for 2- After 5Hr, stir for 5-12Hr at 70-120°C to react to generate the dispersion resin, and/or
  • the mass ratio of the acrylic copolymer Z to the intermediate is 1:1 to 1.5:1.
  • the obtained acrylic copolymer Z and the intermediate are heated and dissolved in a second solvent in the presence of a catalyst and refluxed for 3.5 hours. After that, stir for 8 hours at 90°C to react to generate the dispersion resin, and/or
  • the mass ratio of the acrylic copolymer Z to the intermediate is 1.2:1.
  • the acrylic compound is selected from the group consisting of methacrylic acid, acrylic acid, benzyl acrylate, styrene, methyl methacrylate, and methacrylic acid.
  • Butyl ester isobornyl methacrylate, glycidyl methacrylate, tricyclo[5.2.1.02,6]dec-8-yl methacrylate, hydroxyethyl methacrylate, hydroxybutylacrylate, nitrogen
  • the first solvent and the second solvent are each at least one selected from the group consisting of toluene, ethyl acetate, DMF, NMP, DMSO and acetonitrile, and/or
  • the catalyst is at least one selected from the group consisting of tetramethylguanidine, TMG, KI, NaI, triethylamine and metformin.
  • n-butanol can be re-added, for example, 1.5 times the volume of the original reaction solvent, stirred at, for example, 55°C for, for example, 1Hr, and added to, for example, 3 times the volume.
  • petroleum ether filter and dry the precipitate to obtain dispersion resin.
  • the nanosilver wire photoresist contains the following raw materials in parts by weight: 0.1-10 parts of nanosilver wires, 0.05-5 parts of toner, 0.1-10 parts of dispersion resin, and 0.3-10 parts of developing resin. 20 parts, photo-curable resin 0.4-40 parts, photoinitiator 0.05-0.5 parts, additives 0.05-1 parts and organic solvent 300-1000 parts.
  • the average diameter width D 50 of the silver nanowires is 10-80 nm, and the average length D 50 of the silver nanowires is 3-60 ⁇ m.
  • the preparation method of nano silver wires is to use chemical methods, such as silver nitrate catalyst reduction method to prepare nano silver wires, and then through solvent replacement and adding the dispersion resin of the general formula (1) structure of the present invention to stabilize the nano silver wires.
  • Dispersion stability in organic solvents In order to ensure that the surface resistivity of the single-layer transparent mesh overlap film formed by drying the nanosilver wires at 100°C is in the range of 500-100000m ⁇ / cm2 , the solid content ratio of the dispersion in which it is located is 0.06-0.8 %, as the proportion of nanosilver wires increases, the light transmittance of the film will decrease from 99% to 90%.
  • the particle size of the toner is 5-200 nm, and the toner is selected from the group consisting of peptidocyanine pigments, carbazole pigments, graphene and carbon nanotubes. species or several species.
  • the particle size of the toner is preferably 10-100 nm, more preferably 20-50 nm.
  • the above-mentioned substance with this particle size is pretreated through a hyperdispersant humidification and grinding process to form an organic dispersion slurry with a concentration of 0.001-0.5%, which is added to the above-mentioned dispersion resin containing nanosilver wires and having the structure of general formula (1) In the dispersion slurry, it plays the role of adjusting the b* value and improving yellowing.
  • the developing resin is a copolymer of methacrylic acid and methyl methacrylate, a copolymer of methacrylic acid and cyclohexyl methacrylate, a copolymer of methacrylic acid and glycidyl methacrylate, a copolymer of methacrylic acid and methyl methacrylate.
  • a kind of solid content of the developing resin in the dispersion liquid is 0.3-20%.
  • the average acid value of the developing resin is 60KOH/g-200KOH/g, preferably 90KOH/g-150KOH/g.
  • the photocurable resin is selected from one or more of the following compounds: epoxy soybean oil acrylate, modified epoxy acrylate, polyester acrylate, hexanediol diacrylate (HDDA), trimethylol Propane triacrylate (TMPTA), dipropylene glycol diacrylate (DPGDA), pentaerythritol triacrylate (PETA), pentaerythritol hexaacrylate, pentaerythritol pentaacrylate, and pentaerythritol triacrylate.
  • HDDA hexanediol diacrylate
  • TMPTA trimethylol Propane triacrylate
  • DPGDA dipropylene glycol diacrylate
  • PETA pentaerythritol triacrylate
  • pentaerythritol hexaacrylate pentaerythritol pentaacrylate
  • pentaerythritol triacrylate pentaerythrito
  • the photoinitiators are mainly electroasymmetrically active photoinitiators, such as oxime ester initiators, triazine initiators or heterocyclic initiators.
  • photoinitiators such as oxime ester initiators, triazine initiators or heterocyclic initiators.
  • one of the following structures diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexylphenylmethanone, 2-phenylmethyl-2-(dimethyl Amino)-4'-morpholinobutyrophenone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinpropan-2-one, 2-hydroxy-2-methyl-1 -Phenyl-1-propanone, 2-isopropylthiaxantrone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, o-benzoic acid Methyl ester, 4-methylbenzoph
  • the auxiliary agents are leveling agents and coupling agents.
  • the leveling agents are polyether-modified polydimethylsiloxane solution, polyester-modified polydimethylsiloxane solution, polyether-modified polydimethylsiloxane solution, and polyether-modified polydimethylsiloxane solution.
  • the coupling agent is N'- ⁇ '-aminoethyl-N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxy Silane, N'- ⁇ '-aminoethyl-N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane, N'- ⁇ '-aminoethyl-N- ⁇ -aminoethyl - ⁇ -Aminopropylmethyldiethoxysilane, N'- ⁇ '-aminoethyl-N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N'- ⁇ '-aminoethyl
  • the organic solvent is methyl ethyl ketone, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, 2-ethoxypropanol, 2-methyl Oxypropanol, 3-methoxybutanol, ethyl 3-ethoxypropionate, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, ethyl acetate, isoacetic acid One or two or more of butyl ester, tert-butyl acetate or n-butyl acetate.
  • the preparation method of nano silver wire photoresist can be: after preparing the above materials according to the formula proportion, first add the dispersion resin to the nano silver wire and toner solution to make a dispersion, and use mechanical stirring or ultrasonic dispersion or vibrator Or roller shaker and other equipment to make it into improved yellowing dispersion nano silver slurry; on this basis, add photo-curing resin, photoinitiator, developing resin, additives, continue to use mechanical stirring or ultrasonic dispersion or oscillator or roller Shake machine and other equipment to make it into nano silver photoresist.
  • a touch structure includes a plurality of mutually insulated first conductive groups and a plurality of mutually insulated second conductive groups.
  • the plurality of first conductive groups and the plurality of second conductive groups are arranged in a criss-cross pattern, each of which is
  • a conductive group extends along a first direction and includes a plurality of electrically connected first conductive units.
  • Each second conductive group extends along a second direction and includes a plurality of electrically connected second conductive units.
  • the first direction and the second conductive unit The two directions intersect, and the plurality of first conductive groups and the plurality of second conductive groups are formed of the nanosilver wire photoresist described in any one of the above.
  • the first direction is orthogonal to the second direction, and at the intersection of the first conductive group and the second conductive group, the first conductive group and the second conductive group are An insulating photoresist is disposed therebetween to insulate the first conductive group and the second conductive group from each other.
  • a method for making a touch structure including:
  • a plurality of mutually insulated first conductive groups are formed on the upper surface of the substrate through a photolithography process.
  • Each of the first conductive groups includes a plurality of first conductive groups extending along a first direction.
  • An insulating layer is formed on the substrate through a photolithography process, the insulating layer is located at the intersection of two adjacent first conductive units and covers the intersection;
  • a plurality of mutually insulated second conductive groups are formed on the upper surface of the substrate through a photolithography process.
  • the plurality of first conductive groups and the plurality of second conductive groups are The groups are arranged in a criss-cross pattern.
  • Each second conductive group includes a plurality of electrically connected second conductive units extending along the second direction. The intersection point of two adjacent second conductive units is located on the insulating layer. Above, the first direction and the second direction intersect.
  • a display device containing a touch control structure includes a display, a touch control structure and a cover plate.
  • the touch control structure is the above-mentioned touch control structure.
  • the display is a liquid crystal display, an OLED display or an LED display.
  • the liquid crystal display may include a TFT backplane, a liquid crystal layer, a color filter and a polarizer arranged in sequence from bottom to top.
  • the touch structure is located between the polarizer and the cover of the display and is provided on the polarizer or on the insulating film between the polarizer and the cover.
  • the insulating film is, for example, a PET film, or the touch structure is provided on the color filter. on the TFT backplane and between the polarizer and the color filter, or the touch structure is set on the TFT backplane and between the TFT backplane and the liquid crystal layer.
  • a display device containing a touch structure including:
  • the display includes a polarizer, the upper surface of the polarizer is provided with a plurality of mutually insulated first conductive groups and a first protective layer covering the first conductive groups, each first conductive group extending along the first direction And including a plurality of electrically connected first conductive units, the plurality of first conductive groups are formed of the nanosilver wire photoresist described in any one of the above;
  • Transparent insulating film the lower surface of the transparent insulating film is provided on the first protective layer, the upper surface of the transparent insulating film is provided with a plurality of mutually insulated second conductive groups and a second conductive group covering the second conductive group.
  • Protective layer each second conductive group extends along the second direction and includes a plurality of electrically connected second conductive units, the plurality of first conductive groups and the plurality of second conductive groups are arranged in a criss-cross direction, the first direction Intersecting with the second direction, the plurality of second conductive groups are formed by the nanosilver wire photoresist described in any one of the above;
  • a cover plate is provided on the second protective layer.
  • the display is a liquid crystal display, an OLED display or an LED display.
  • the beneficial effects of the present invention at least include:
  • the nano-silver wire photoresist of the present invention adopts the dispersion resin of the above-mentioned novel structure.
  • the dispersion resin can be used to disperse and moisten nano-silver wires in a variety of organic solvents, replacing hyperdispersant solvents and improving dispersion stability. Due to the role of sex, the nano-silver wire photoresist has excellent dispersion and stability, good fluidity and high light transmittance, low viscosity, and good coating performance.
  • the obtained nano-silver wire photoresist has excellent The viscosity is lower than 30mPa.s, 23°C/50rpm, and the rheological r value is between 0.95 and 1.03, showing good coatability.
  • the above-mentioned nanosilver wire photoresist can produce fine transparent conductive lines below 10 ⁇ m under the yellow light process, and its sheet resistance is in the range of 20-100 ohms, which can realize large-size capacitive touch screens.
  • Manufacturing can replace ITO metal grid capacitor materials to produce various types of transparent touch circuits, especially in flexible touch displays, it overcomes the shortcomings of ITO that is not resistant to bending, and the nano-silver wire photoresist of the present invention can realize the yellow light process
  • the process can directly etch various types of corresponding transparent conductive patterns, which can overcome the poor and complicated processes of ITO or metal grid coating and etching to make transparent electrodes, as well as the traditional water-based nano silver wire ink coating and laser engraving process to make transparent electrodes. defect.
  • the nano silver wire photoresist of the present invention can realize the yellow light process technology to directly conduct electrode wiring on the gallium nitride semiconductor, avoiding the previous coating of ITO and etching or laser engraving and other severe physical and chemical conditions such as high temperature and strong acid. risk, thus improving the manufacturability of Micro-LED displays while contributing to the environmental protection requirements of the process.
  • nanosilver wire photoresist of the present invention to photolithograph touch circuits on base films such as polarizers, a touch screen that can be used to display integrated touch sensors can be obtained.
  • a display can be manufactured in which a touch sensor is integrated on the polarizer film layer on the upper surface of the display.
  • Figure 1 is a partial enlarged view of a touch capacitive pattern for a "diamond-shaped" single-layer touch screen manufactured using the nanosilver wire photoresist in Embodiment 6 of the present invention.
  • FIG. 2 is a schematic diagram of a touch structure according to an embodiment of the present invention.
  • Figure 3 is a schematic cross-sectional view of a display device according to an embodiment of the present invention.
  • Figure 4 is a schematic cross-sectional view of a display device according to another embodiment of the present invention.
  • Figure 5 is a schematic cross-sectional view of a display device according to another embodiment of the present invention.
  • 101 represents the display
  • 102 represents the polarizer on the upper surface of the display
  • 103 represents the "bridge" type nano silver wire photoresist transparent conductive pattern in the x and y directions.
  • Type layer represents the OCA bonding layer
  • 105 represents the cover layer.
  • Figure 6 is a schematic cross-sectional view of a display device according to another embodiment of the present invention.
  • 201 represents a display
  • 202 represents a polarizer with a y-direction nano silver line photoresist transparent conductive pattern layer
  • 203 represents an OCA laminating adhesive layer
  • 204 Indicates a PET film with a transparent conductive pattern layer of x-direction nano silver wire photoresist
  • 205 indicates the OCA laminating adhesive layer
  • 206 indicates the cover layer.
  • Examples 1 to 5 are methods for preparing dispersion resin according to the present invention.
  • the reagents involved in the following examples can all be obtained through market purchase.
  • a dispersion resin whose preparation method is as follows:
  • Oligomer synthesis 15g of 2-acrylic acid-2hydroxy-3-phenoxypropyl ester, 4.47g of methacrylic acid, 5.41g of styrene; 0.5g of free radical initiator azobisisobutyronitrile; chain transfer 0.9g of ⁇ -methylstyrene linear dimer as an agent; added to 60g of solvent propylene glycol dimethyl ether; under nitrogen atmosphere, heated to 90°C, stirred at 300rpm for 4Hr, and carried out free radical reaction to synthesize oligomer intermediate Z-1, after characterization, the Mw value of oligomer intermediate Z-1 is 5000-10000; the Pd value is within 2.5; the viscosity is ⁇ 5000cps;
  • a dispersion resin whose preparation method is as follows:
  • the dispersion resin 1-2 of (1) has been characterized.
  • the Mw value of the dispersion resin 1-2 is 20350; the Pd value is 2.3).
  • a dispersion resin whose preparation method is as follows:
  • Oligomer synthesis 15g of 2-acrylic acid-2hydroxy-3-phenoxypropyl ester, 4.47g of methacrylic acid, 5.2g of methyl methacrylate, and 7.4g of benzyl methacrylate; free radical initiator 0.6g of azobisisobutyronitrile; 1.05g of chain transfer agent ⁇ -methylstyrene linear dimer; add to 60g of solvent ethyl acetate; under nitrogen atmosphere, heat to 80°C and stir at 300rpm for 4Hr. Carry out free radical reaction to synthesize oligomer intermediate Z-3. After characterization, the Mw value of oligomer intermediate Z-3 is 5000-10000; the Pd value is within 2.5; the viscosity is ⁇ 5000cps;
  • a dispersion resin whose preparation method is as follows:
  • a dispersion resin whose preparation method is as follows:
  • Oligomer synthesis 15g of 2-acrylic acid-2hydroxy-3-phenoxypropyl ester, 4.47g of methacrylic acid, 5.41g of styrene, 11.55g of isobornyl methacrylate; free radical initiator azo 0.8g diisobutyronitrile; 1.05g chain transfer agent ⁇ -methylstyrene linear dimer; add to 65g solvent ethyl acetate; under nitrogen atmosphere, heat to 90°C, stir at 300rpm for 4Hr, and proceed freely Oligomer intermediate Z-5 was synthesized through base reaction. After characterization, the Mw value of oligomer intermediate Z-5 was 5000-10000; the Pd value was within 2.5; the viscosity was ⁇ 5000cps;
  • the dispersion resin 1-5 of 1) has been characterized.
  • the Mw value of the dispersion resin 1-5 is 19584; the Pd value is 2.1.
  • nanosilver wire toner
  • dispersion resin developing resin
  • photocurable resin photoinitiator
  • auxiliary agent organic solvent
  • the toner in the following Table 1 is a graphene dispersion slurry with a concentration of 1%
  • the dispersion resin is the dispersion resin in Examples 1-5
  • the developing resin is a methacrylic acid-styrene-maleic anhydride copolymer, which is photocured.
  • the resin is DPPA
  • the photoinitiator is 1-hydroxycyclohexyl phenyl ketone
  • the additive is fluorocarbon additive, for example, EFKA3883 can be used
  • the organic solvent A is butyl acetate, for example, n-butyl ester, isobutyl ester and One or a combination of several tert-butyl esters
  • organic solvent B is ethyl 3-ethoxypropionate.
  • the specific ratio is shown in the component formula of nano silver wire photoresist in Table 1.
  • Table 1 shows that the present invention can produce conductive transparent patterns through the photolithography process, and the silver wire dispersion effect is further improved compared to the existing inventions, and no agglomeration occurs.
  • nano-silver wire photoresist When preparing the nano-silver wire photoresist, first put the nano-silver wire into part of the organic solvent A, then add toner and dispersion resin to mix to form a dispersion; then add photo-curing resin, photo-initiator, developing resin Dissolve the additives and additives in organic solvent B at 50-80°C, then cool to 25°C and add the above dispersion, and use one or more of mechanical stirring or ultrasonic dispersion or oscillator or roller shaker and other equipment Combine to mix thoroughly, then purify and fill, store at 0-5°C.
  • the “diamond” type single-layer touch screen touch capacitive pattern manufactured by using the nano silver wire photoresist and OC photoresist in the above embodiments 6-12 is as shown in Figure 1.
  • the line width and line spacing in Figure 1 Ratio: L/S is 30 ⁇ m. Analyze and compare its performance parameters. The test results are shown in Table 2.
  • ⁇ means that the line has not fallen off, but the alignment patch mark (Marker) has fallen off. ⁇ means that neither the line nor the marker has fallen off.
  • the present invention can obtain a conductive pattern with high resolution (high precision), high transmittance, low haze, strong adhesion to the substrate and low surface resistivity. Furthermore, this type of conductive pattern was tested after being bound to the IC by FPC and then powered on. After the UV1000Hr resistance and double 85 high temperature and humidity 500Hr reliability tests, the resistance value still remained unchanged; compared with the touch sensor made of traditional nano-silver wire materials , overcoming the phenomenon of insufficient reliability such as Ag migration.
  • the present invention also provides a touch structure, including a plurality of mutually insulated first conductive groups 10 and a plurality of mutually insulated second conductive groups 20 , the plurality of first conductive groups 10 and a plurality of third conductive groups 20 .
  • the two conductive groups 20 are arranged in a criss-cross pattern.
  • Each first conductive group 10 extends along the first direction and includes a plurality of electrically connected first conductive units 11.
  • Each first conductive group 10 is led outward through wires.
  • the second conductive group 20 extends along the second direction and includes a plurality of electrically connected second conductive units 21.
  • Each second conductive group 20 is led outward through wires.
  • the first direction and the second direction intersect, preferably are orthogonal.
  • the plurality of first conductive groups 10 and the plurality of second conductive groups 20 are formed of the nanosilver wire photoresist of the present invention. At the intersection of the first conductive group 10 and the second conductive group 20, an insulating photoresist is disposed between the first conductive group 10 and the second conductive group 20 to make the first conductive group 10 and the second conductive group Groups 20 are insulated from each other.
  • the manufacturing method of the above touch structure may include:
  • a plurality of mutually insulated first conductive groups 10 are formed on the upper surface of the substrate through a photolithography process.
  • the substrate can be a TFT backplane 1, a color filter 3 or a polarizer 4.
  • Each of the first conductive groups 10 includes a plurality of electrically connected first conductive units 11 extending along the first direction.
  • An insulating layer (not shown) is formed on the substrate through a photolithography process.
  • the insulating layer can be formed by OC photoresist.
  • the insulating layer is located at the intersection of two adjacent first conductive units 11 and covers it. The meeting point.
  • each of the second conductive groups 20 includes a plurality of electrically connected second conductive units 21 extending along the second direction.
  • the intersection point of two adjacent second conductive units 21 is located on the On the insulating layer, the first direction and the second direction are preferably orthogonal to each other.
  • the present invention also provides a display device containing a touch structure.
  • the display device includes a display, a touch structure and a cover 5.
  • the touch structure is the above-mentioned touch structure, and the display can be a liquid crystal display. , OLED display or LED display.
  • the display device specifically includes a display 101, a polarizer 102 on the upper surface of the display 101, and a “bridge” nanosilver wire photoresist transparent conductive pattern in the x and y directions on the polarizer 102.
  • the x and y directions of the layer 103, the OCA adhesive layer 104 and the cover layer 105 on the conductive pattern layer 103 can be vertical.
  • the display device specifically includes a display 201, a polarizer 202 with a y-direction nano silver line photoresist transparent conductive pattern layer on the upper surface of the display 201, and an OCA adhesive layer 203 , a PET film 204 with a transparent conductive pattern layer of nano-silver wire photoresist in the x direction, an OCA bonding adhesive layer 205 and a cover layer 206 on the PET film 204.
  • the x and y directions can be vertical.
  • the display device when the display is a liquid crystal display, the display device may be an In-Cell type, On-Cell type or OGS-like display device.
  • the liquid crystal display includes a TFT backplane 1, a liquid crystal layer 2, a color filter 3 and a polarizer 4 arranged in sequence from bottom to top.
  • the touch structure is provided on the polarizer 4 and located between the polarizer 4 and the polarizer 4. between the cover plates 5 to form an OGS-like display device, or the touch structure is provided on the color filter 3 and between the polarizer 4 and the color filter 3 to form an On-Cell display device, or
  • the touch structure is disposed on the TFT backplane 1 and is located between the TFT backplane 1 and the liquid crystal layer 2 to form an In-Cell display device.
  • the present invention also provides another display device containing a touch structure, including: a display, a transparent insulating film 6 and a cover 5 .
  • the display is a liquid crystal display, an OLED display or an LED display.
  • the display includes a polarizer 4.
  • the upper surface of the polarizer 4 is provided with a plurality of mutually insulated first conductive groups 10 and a first protection covering the first conductive groups 10. layer (not shown), each first conductive group 10 extends along the first direction and includes a plurality of electrically connected first conductive units 11.
  • the plurality of first conductive groups 10 are made of the nanosilver wire photoresist of the present invention.
  • the lower surface of the polarizer 4 can be disposed on the color filter 3 using a full lamination process.
  • the transparent insulating film 6 may be a PET film.
  • the lower surface of the transparent insulating film 6 is disposed on the first protective layer.
  • the upper surface of the transparent insulating film 6 is disposed with a plurality of mutually insulated second conductive groups 20 and A second protective layer (not shown) covering the second conductive groups 20.
  • Each second conductive group 20 extends along the second direction and includes a plurality of electrically connected second conductive units 21.
  • the plurality of first conductive units 21 The group 10 and the plurality of second conductive groups 20 are arranged in a criss-cross manner, and the first direction and the second direction intersect.
  • the plurality of second conductive groups 20 are formed of the nanosilver wire photoresist of the present invention.
  • the cover plate 5 is disposed on the second protective layer and can be completed using a full lamination process. At this time, the touch structure can be disposed on the transparent insulating film 6 , and the transparent insulating film 6 can be a PET film.
  • a method of manufacturing an OGS-like double-layer transparent conductive layer patterned touch structure on the upper surface of a polarizer based on the nano-silver photoresist which is prepared using the following steps:
  • Substrate processing The cut-to-size polarizer (the polarizer is used as the substrate) is fixed by vacuum attachment, so that the substrate is spread horizontally on the operating table;
  • Coating Coating the first layer of the nano-silver wire photoresist on the substrate using slit method
  • Pre-baking The coated substrate is baked at 60-80°C for 2-4 minutes;
  • Exposure Add mask exposure to form a pitch-shaped transparent mask "bridge" pattern with a thickness of 0.08-0.4 ⁇ m and a line width of 10-30 ⁇ m on the substrate, with an energy of 50-300mj/cm 2 ;
  • Post-baking Bake at 80-140°C for 15-30 minutes;
  • step 3 Make an insulating photoresist "bridging" pattern layer.
  • step 5) Make the packaging protective layer: Slit-coat the second layer of the low-temperature OC photoresist on the substrate in step 4) to form a transparent weather-resistant protective layer with a thickness of 0.3-1 ⁇ m, and leave a connection IC on the edge FPC wiring position; and then go through pre-baking, exposure, development and post-baking in sequence.
  • the above processing method is the same as step 2).
  • a method of manufacturing an On-Cell touch structure using the nano-silver photoresist including the following steps in sequence:
  • CF substrate (color filter) processing Coat a protective layer with a thickness of 1 ⁇ m on the surface of the color pixel layer of the CF substrate, and then use vacuum attachment and fixation on the surface to spread the CF substrate horizontally on the operating table;
  • Exposure Apply mask exposure to form a rectangular transparent conductive "bridge" pattern with a thickness of 0.08-0.4 ⁇ m on the substrate, and the energy is 100-300mj/cm 2 ;
  • step 3 Make the insulating photoresist "bridging" pattern layer: Coat the first layer of OC photoresist on the conductive "bridging" pattern in step 2), and then perform pre-baking, exposure, development and post-baking in sequence. Processing method Same as step 2) above; finally, a layer of transparent insulating rectangular pattern with a thickness of 0.5-1.2 ⁇ m is formed, and the insulating photoresist "bridge” in the x direction must completely cover the conductive "bridge” and the conductive "bridge” in the y direction Both ends are completely exposed from the "bridge” of the insulating photoresist, and the vacuum is -0.1MPa;
  • step 3 Coat the second layer of the nano-silver wire photoresist on the substrate in step 3), and sequentially go through the steps of vacuum, pre-baking, exposure, development and post-baking to form 0.08-0.4 ⁇ m thick "rhombus” electrode layer, and is continuously conductive in the width direction through the "rhombus” electrode layer on top of the insulating "bridge", and is passed through the "rhombus” electrode layer on the top of the insulating "bridge” in the length direction. Engraving and developing partitions; the processing methods of vacuum, pre-baking, exposure, development and post-baking pass through step b;
  • step 5 Make a packaging protective layer: Coat the second layer of the OC photoresist on the substrate in step 4), and then go through vacuum, pre-baking, exposure, development and post-baking in order to form a layer of 0.3-1 ⁇ m thickness transparent and resistant layer. Thermal weather-resistant protective layer, and the FPC wiring position for connecting the IC can be left on the edge; the processing methods of vacuum, pre-baking, exposure, development and post-baking are the same as step 2).
  • a method of manufacturing Micro-LED transparent anodes and display touch devices using the On-Cell touch structure which is prepared in either of the following two ways:
  • Method 1 includes the following steps:
  • Coating Coat a layer of the nano-silver wire photoresist on the pixel surface of the blue Micro-LED in a vacuum of -0.1MPa;
  • Exposure Expose with a mask to form a layer of pixel-level transparent conductive pattern with a top thickness of 0.1-0.2 ⁇ m, and then overlay and engrave with energy 100-300mj/cm 2 ;
  • Post-baking Bake at 120-240°C for 30 minutes;
  • step 2) Make the packaging protective layer: Coat a layer of OC photoresist on the anode wiring pattern layer in step 1), and then go through vacuum, pre-baking, exposure, development and post-baking in order to form a layer of 0.3-0.5 ⁇ m thickness
  • the protective layer the processing methods of vacuum, pre-baking, exposure, development and post-baking are the same as step 1);
  • step 3 Align and bond the On-Cell touch CF substrate: Make a layer of OCA optical glue on the protective layer in step 2), and laminate the On-Cell touch device and the OCA optical glue together to achieve Manufacturing of this new full-color touch display.
  • Method 2 includes the following steps:
  • Coating Coat a layer of the nano-silver wire photoresist on the pixel matrix of the blue Micro-LED, vacuum -0.1MPa;
  • Exposure Apply mask exposure to form a conductive matrix with a thickness of 1-3 ⁇ m and a width of 5-10 ⁇ m at the matrix, and then overlay the alignment with an energy of 100-300mj/cm 2 ;
  • Post-baking Bake at 120-240°C for 30 minutes;
  • step 2) Make the packaging protective layer: Coat a layer of OC photoresist on the anode wiring pattern layer in step 1), and then go through vacuum, pre-baking, exposure, development and post-baking in order to form a layer of 0.3-0.5 ⁇ m thickness of the protective layer; the processing methods of vacuum, pre-baking, exposure, development and post-baking are the same as step 1);
  • step 3 Align and bond the On-Cell touch CF substrate: Make a layer of OCA optical glue on the protective layer in step 2), and laminate the On-Cell touch device and the OCA optical glue together to achieve Manufacturing of this new full-color touch display.
  • a double-sided touch sensor device in which a single-layer transparent conductive layer pattern is manufactured on the upper surface of the polarizer based on the nano-silver wire photoresist and is bonded to a PET film with a single-layer transparent conductive layer pattern on the surface. Prepared using the following steps:
  • Roll coating process Unroll the upper surface of the roll of polarizer (polarizer as the substrate) through the roll to roll coating line;
  • Coating Coat a layer of the nano-silver wire photoresist on the substrate using a roll to roll continuous coating method
  • Pre-baking Bake in the drying tunnel at 60-80°C for 2-4 minutes;
  • Exposure Add a mask and expose on a layer of nano-silver wire photoresist film with a thickness of 0.04-0.4 ⁇ m formed after exiting the drying tunnel, and expose the mask pattern with an energy of 50-300mj/cm 2 ;
  • Post-baking Bake for 15-20 minutes under drying tunnel conditions of 80-140°C, and then roll up;
  • step 3 Make the packaging protective layer: roll to roll and apply a layer of low-temperature OC photoresist on the roll material in step 2) to form a transparent weather-resistant protective layer with a thickness of 0.3-1 ⁇ m, and leave connections at the edges FPC wiring position of the IC; then go through pre-baking, exposure, development, post-baking (the above processing method is the same as step 2) and cutting;
  • Coating Use roll to roll continuous coating method to coat a layer of the nano silver wire photoresist on the PET substrate;
  • Exposure Add a mask and expose on a nano-silver wire photoresist film with a thickness of 0.04-0.4 ⁇ m after exiting the drying tunnel, and expose the mask pattern with an energy of 50-300mj/cm 2 ;
  • Post-baking Bake for 15-20 minutes under drying tunnel conditions of 80-140°C, and then roll up;
  • step 5 Make the packaging protective layer: roll to roll and apply a layer of low-temperature OC photoresist on the roll material in step 4) to form a transparent weather-resistant protective layer with a thickness of 0.3-1 ⁇ m, and leave connections at the edges FPC wiring position of the IC; then go through pre-baking, exposure, development, post-baking (the above processing method is the same as step 2) and cutting;
  • a method of manufacturing an OGS-like double-layer transparent conductive layer patterned touch sensor device on the upper surface of a PET substrate based on the nano-silver photoresist which is prepared using the following steps:
  • Coating Apply a layer of the nano-silver wire photoresist on the substrate using a roll to roll continuous coating method
  • Pre-baking Bake in the drying tunnel for 2-4 minutes at 60-80°C;
  • Exposure Add a mask and expose a layer of nano-silver line photoresist film with a thickness of 0.04-0.4 ⁇ m after exiting the drying tunnel to expose a pitch-shaped mask "bridge" pattern with a line width of 10-30 ⁇ m. 50-300mj/cm 2 ;
  • Post-baking Bake for 15-20 minutes under drying tunnel conditions of 80-140°C, and then roll up;
  • step 3 Make an insulating photoresist "bridging" pattern layer.
  • step 5 Make the packaging protective layer: roll to roll and apply a layer of low-temperature OC photoresist on the roll material in step 4) to form a transparent weather-resistant protective layer with a thickness of 0.3-1 ⁇ m, and leave connections at the edges FPC wiring position of the IC; then go through pre-baking, exposure, development, and post-baking in sequence (the above processing method is the same as step 2), and then cut and bind the IC.
  • the upper surface of the polarizer bound to the IC has an OGS-like double-layer transparent conductive layer pattern, and the lower surface of the polarizer and the upper surface of the display are bonded together through a laminating process. Furthermore, the upper surface of the display and the cover plate are bonded together through a lamination process, and the cover plate covers the double-layer transparent conductive layer pattern, thereby obtaining a display and touch integrated device.
  • the upper surface of the polarizer bound to the IC has a single-layer transparent conductive layer pattern
  • the upper surface of the PET film bound to the IC has a single-layer transparent conductive layer pattern.
  • the lower surface of the polarizer is The surface and the upper surface of the display are bonded together through a laminating process.
  • the lower surface of PET is bonded to the upper surface of the polarizer.
  • the upper surface of PET and the cover are bonded together through a bonding process.
  • the cover plate covers the PET.
  • the single-layer transparent conductive layer pattern on the upper surface of the film is used to obtain a display and touch integrated device.

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Abstract

本发明公开了一种纳米银线光阻剂，包括纳米银线和分散树脂，分散树脂由式（1）表示：（Z-A） n-R m （1），式（1）中，n＝1-5，m＝1-5，且n+m≤6；Z表示H，或含有氨基、环氧基、具有1～14个碳原子的烷基、具有3～14个碳原子的环烷基或芳基取代基的丙烯酸类共聚物；R表示C、N、CH基团、式（A）或含有2-14个碳原子的直链烷基、2-14个碳原子的脂肪环烷基、3-14个碳原子的芳基和杂芳基中的至少一种；A由式（2）表示：式（2）中，W与Z连接，羧基与R连接。

Description

纳米银线光阻剂、触控结构和显示装置 技术领域
本发明涉及光阻剂技术领域，尤其涉及包括纳米银线和分散树脂的纳米银线光阻剂以及使用了该纳米银线光阻剂的触控结构和显示装置。
背景技术
触摸显示屏是以智能手机为代表的各类智能显示触控终端最重要的器件之一，触摸显示屏是实现人机交互、多媒体信息传递的终端硬件。
但是，对于以65寸以上的大屏触控电教为代表的商用一体化大屏显示，例如触控显示电教一体化会议机，触控控制是一个重要瓶颈技术。具体原因是，现有最成熟的触控电容材料ITO，在超过32寸的触控传感器尺寸时，由于ITO的电阻率不能很好的降低到100欧姆/电阻以下，导致触控驱动芯片无法有效的传递触摸信号，导致触控操作体验不良。
对于商用一体机的制造来说，如果能把触控传感器集成在盖板表面，或者是显示器的表面，不仅减少了整机的结构层数，随之而来带来光学性能提升。
现有的一种方法使用纳米银线光阻剂来制作触控层，存在的问题是，纳米银线容易团聚絮凝，导致纳米银线光阻剂可涂布性达不到要求，进而导致制作的透明导电线条不够精细，影响触控效果。
发明内容
为了克服现有技术的不足，本发明的目的之一在于提供一种纳米银线光阻剂，该纳米银线光阻剂具有良好的导电性和高的光透过率，并且粘度低、涂布性能好，在制作触控结构和应用在触控显示一体化器件上时，能够替代ITO制作各类透明电极，且电阻降低，尤其克服了ITO不耐弯曲的缺点，在柔性触摸显示方面具有良好的表现。本发明的目的之二在于提供一种触控结构及其制造方法，通过该触控结构获得触控效果灵敏、实现可弯曲的柔性触控，并且减少了制程流程和成本的作用。
本发明的目的之三在于提供一种含有触控结构的显示装置及其制造方法，通过该显示装置获得触控效果灵敏、实现可弯曲的柔性触控，并且减少了制程流程和成本。
本发明的目的采用以下技术方案实现：
一种纳米银线光阻剂，包括纳米银线和分散树脂，分散树脂的作用为稳定流变和抗团聚絮凝，所述分散树脂由式(1)表示：
(Z-A) n-R m            (1)，
其中，在式(1)中，n＝1-5，m＝1-5，且n+m≤6；
Z表示H，或含有氨基、环氧基、具有1～14个碳原子的烷基、具有3～14个碳原子的环烷基或芳基取代基的丙烯酸类共聚物；
R表示C、N、CH基团、
Figure PCTCN2022101145-appb-000001
或含有2-14个碳原子的直链烷基、2-14个碳原子的脂肪环烷基、3-14个碳原子的芳基和杂芳基中的至少一种；
A由式(2)表示：
Figure PCTCN2022101145-appb-000002
并且在式(2)中，W与Z连接，羧基与R连接，W表示H原子、具有1～14个碳原子的取代或未取代的烷基、具有2～6个碳原子的环氧烷基、具有3～14个碳原子的取代或未取代的芳基和取代或未取代的杂芳基中的至少一种。
分散树脂为具有上述结构的端基低聚物分子分散剂，该分散树脂分子端基为甲基丙烯酸与苯乙烯共聚物、聚酯共聚物、聚氨酯共聚物、环氧树脂共聚物、羟乙基纤维素醚、羟丙基甲基纤维素、甲基羟乙基纤维素醚或聚乙烯醇缩丁醛中的一种或两种及以上。在分散液当中的固含量占比为0.1-20％，优选1-10％，更优选2-5％。
在一些可选实施例中，n＝1-3，m＝1-3，且n+m≤4，和/或
Z表示选自由甲基丙烯酸、丙烯酸、丙烯酸苄酯、苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸异冰片酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸三环[5.2.1.02,6]癸-8-基酯、甲基丙烯酸羟乙酯、羟丁基丙烯酸酯、氮苯基马来酰亚胺、马来酸酐、2-丙烯酸-2羟基-3-苯氧基丙酯或季戊四醇丙烯酸酯所组成的组中的一种以上化合物所形成的共聚物，和/或
W表示H、甲基、乙基、羟基取代的烷基、环氧烷基、苯基、苄基、酚基中的至少一种。
在一些可选实施例中，A表示由下列各式所表示的化合物中的至少一种：
Figure PCTCN2022101145-appb-000003
上述分散树脂可以采用以下制备方法得到，包括以下步骤：
在自由基引发剂的作用下，将含有氨基、环氧基、具有1～14个碳原子的烷基、具有3～14个碳原子的环烷基或芳基取代基的丙烯酸类化合物加入到含链转移剂的第一溶剂中，在惰性气氛下，通过自由基溶液聚合反应，生成丙烯酸类共聚物Z；
将所获得的丙烯酸类共聚物Z与中间体在催化剂的存在下，在第二溶剂中进行反应， 以生成分散树脂。
用于制备所述分散树脂的中间体由式(3)表示：
(X-A) n-R m              (3)，
其中，在式(3)中，X表示卤素；
n＝1-5，m＝1-5，且n+m≤6；
R表示C、N、CH基团、
Figure PCTCN2022101145-appb-000004
或含有2-14个碳原子的直链烷基、2-14个碳原子的脂肪环烷基、3-14个碳原子的芳基和杂芳基中的至少一种；
A由式(2)表示：
Figure PCTCN2022101145-appb-000005
并且在式(2)中，W与X连接，羧基与R连接，W表示H原子、具有1～14个碳原子的饱和或不饱和烷基、具有2～6个碳原子的环氧基、具有3～14个碳原子的取代或未取代的芳基和取代或未取代的杂芳基中的至少一种。式中的波浪线用于表示连接其他基团。
在一些可选的实施例中，X为Cl、Br或I，
n＝1-3，m＝1-3，且n+m≤4，和/或
W表示H、甲基、乙基、羟基取代的烷基、环氧烷基、苯基、苄基、酚基中的至少一种。在一些可选的实施例中，所述中间体为以下各式所表示的化合物中的一种：
Figure PCTCN2022101145-appb-000006
Figure PCTCN2022101145-appb-000007
Figure PCTCN2022101145-appb-000008
Figure PCTCN2022101145-appb-000009
如上所述，式(3-1)～(3-12)中，X表示卤素，优选为Cl、Br或I，更优选为Br。
在一些可选的实施例中，在本发明的分散树脂的制备方法中，将所获得的丙烯酸类共聚物Z与所述中间体在催化剂的存在下，在第二溶剂中加热溶解回流2-5Hr之后，在70～120℃，搅拌5～12Hr进行反应，以生成所述分散树脂，和/或
所述丙烯酸类共聚物Z与所述中间体的质量比为1:1～1.5:1。
在一些可选的实施例中，在本发明的分散树脂的制备方法中，将所获得的丙烯酸类共聚物Z与所述中间体在催化剂的存在下，在第二溶剂中加热溶解回流3.5Hr之后，在90℃，搅拌8Hr进行反应，以生成所述分散树脂，和/或
所述丙烯酸类共聚物Z与所述中间体的质量比为1.2:1。
在一些可选的实施例中，在本发明的分散树脂的制备方法中，所述丙烯酸类化合物为选自由甲基丙烯酸、丙烯酸、丙烯酸苄酯、苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸异冰片酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸三环[5.2.1.02,6]癸-8-基酯、甲基丙烯酸羟乙酯、羟丁基丙烯酸酯、氮苯基马来酰亚胺、马来酸酐、2-丙烯酸-2羟基-3-苯氧基丙酯或季戊四醇丙烯酸酯所组成的组中的一种以上化合物，和/或
所述第一溶剂和所述第二溶剂各自为选自由甲苯、乙酸乙酯、DMF、NMP、DMSO和乙腈所组成的组中的至少一种，和/或
所述催化剂为选自由四甲基胍、TMG、KI、NaI、三乙胺和二甲双胍所组成的组中的至少一种。
在一些可选的实施例中，反应结束后，旋转蒸发完溶剂，可以重新加入例如原反应溶剂体积1.5倍量的正丁醇，在例如55℃下搅拌例如1Hr，投加至例如3倍量的石油醚中，将沉淀物抽滤干燥，即可得到分散树脂。
在一些可选实施例中，纳米银线光阻剂包含以重量份计的以下原料：纳米银线0.1-10份、调色剂0.05-5份、分散树脂0.1-10份、显影树脂0.3-20份、光固化树脂0.4-40份、光引发剂0.05-0.5份、助剂0.05-1份和有机溶剂300-1000份。
在一些可选实施例中，所述纳米银线的平均线径宽度D 50为10-80nm，所述纳米银线的平均长度D 50为3-60μm。
纳米银线的制备方法是采用化学法制作加工，例如：硝酸银催化剂还原法制备的纳米银线，再经过溶剂置换及加入本发明的通式(1)结构的分散树脂，以稳定纳米银线所在有机溶剂中的分散稳定性。为了使纳米银线在100℃温度烘干后形成的单层透明网状搭接薄膜表面的电阻率在500-100000mΩ/cm 2范围内，其所在分散液当中的固含量占比为 0.06-0.8％，随着纳米银线占比上升，薄膜的透光率将从99％下降到90％。
在一些可选实施例中，所述调色剂的粒径为5-200nm，且所述调色剂选自由肽菁颜料、咔唑类颜料、石墨烯和碳纳米管组成的组中的一种或几种。
所述调色剂的粒径优选为10-100nm，更优选为20-50nm。具有该粒径尺寸的上述物质，通过超分散剂加湿法研磨工艺预处理成一种有机分散浆，浓度为0.001-0.5％，添加到上述含纳米银线和具有通式(1)结构的分散树脂的分散浆之中，起到调节b*值、改善黄变的作用。
所述显影树脂为甲基丙烯酸与甲基丙烯酸甲酯共聚物、甲基丙烯酸与甲基丙烯酸环己酯共聚物、甲基丙烯酸与甲基丙烯酸环氧丙氧酯共聚物、甲基丙烯酸与甲基丙烯酸-2-羟基乙酯共聚物、甲基丙烯酸-苯乙烯-马来酸酐共聚物、甲基丙烯酸与甲基丙烯酸环己酯或苯乙烯和甲基丙烯酸-2-羟基乙酯共聚物中的一种，所述显影树脂在分散液中的固含量占比为0.3-20％。所述显影树脂的平均酸值为60KOH/g-200KOH/g，优选90KOH/g-150KOH/g。
所述光固化树脂选自下述化合物中的一种或多种：环氧大豆油丙烯酸酯、改性环氧丙烯酸酯、聚酯丙烯酸酯、己二醇二丙烯酸酯(HDDA)、三羟甲基丙烷三丙烯酸酯(TMPTA)、二丙二醇二丙烯酸酯(DPGDA)、季戊四醇三丙烯酸酯(PETA)、季戊四醇六丙烯酸酯、季戊四醇五丙烯酸酯、季戊四醇三丙烯酸酯。
所述光引发剂主要是以电不对称活性的光引发剂为主，肟酯引发剂、三嗪类引发剂或杂环引发剂。优选自以下结构中的一种：氧化二苯基(2,4,6-三甲基苯甲酰基)膦、1-羟基环己基苯基甲酮、2-苯甲基-2-(二甲氨基)-4'-吗啉代丁酰苯、2-甲基-1-[4-甲硫基苯基]-2-吗啉丙烷-2-酮、2-羟基-2-甲基-1-苯基-1-丙酮、2-异丙基硫杂蒽酮、4-二甲基氨基苯甲酸乙酯、4-二甲氨基苯甲酸菜2-乙基己酯、邻苯甲酰苯甲酸甲酯、4–甲基二苯甲酮以及下述式(6-1)至(6-7)表示的化合物。
Figure PCTCN2022101145-appb-000010
Figure PCTCN2022101145-appb-000011
所述助剂为流平剂和偶联剂，所述流平剂为聚醚改性聚二甲基硅氧烷溶液、聚酯改性聚二甲基硅氧烷溶液、聚醚改性聚硅氧烷溶液、聚酯改性聚甲基烷基硅氧烷溶液、聚醚改性聚二甲基硅氧烷溶液、聚醚改性聚二甲基硅氧烷溶液、聚丙烯酸酯溶液或氟碳共聚物溶液中的一种或两种及以上；所述偶联剂为N’-β’-氨乙基-N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷、N’-β’-氨乙基-N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷、N’-β’-氨乙基-N-β-氨乙基-γ-氨丙基甲基二乙氧基硅烷、N’-β’-氨乙基-N-β-氨乙基-γ-氨丙基三甲氧基硅烷、N’-β’-氨乙基-N-β-氨乙基-γ-氨丙基三乙氧基硅烷和N’-β’-氨乙基-N-β-氨乙基-α-氨甲基三乙氧基硅、γ-环己胺丙基三乙氧基硅烷和甲基、γ-环已胺丙基二甲氧基硅烷或γ-氯丙基三乙氧基硅烷(γ2)中的一种或两种及以上。
所述有机溶剂为甲乙酮、乙基溶纤剂、乙二醇二甲醚、乙二醇二乙醚、丙二醇二甲醚、二乙二醇二甲醚、2-乙氧基丙醇、2-甲氧基丙醇、3-甲氧基丁醇、3-乙氧基丙酸乙酯、环己酮、环戊酮、丙二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、乙酸乙酯、乙酸异丁酯、乙酸叔丁酯或乙酸正丁酯中的一种或两种及以上。
纳米银线光阻剂的制备方法可以是，将以上材料按照配方比例配备后，先将分散树脂加入纳米银线和调色剂溶液当中，制成分散液，使用机械搅拌或超声分散或震荡仪或辊摇机等设备将其制成改善黄变分散纳米银线浆；在此基础上加入光固化树脂、光引发剂、显影树脂、助剂，继续使用机械搅拌或超声分散或震荡仪或辊摇机等设备，将其制成纳米银光阻剂。
一种触控结构，包括多个相互绝缘的第一导电组和多个相互绝缘的第二导电组，所述多个第一导电组和多个第二导电组呈纵横交错设置，每一第一导电组沿第一方向延伸且包括多个电性连接的第一导电单元，每一第二导电组沿第二方向延伸且包括多个电性连接的第二导电单元，第一方向和第二方向交叉，所述多个第一导电组和多个第二导电组由上述任一项所述的纳米银线光阻剂形成。
在一些可选实施例中，所述第一方向与所述第二方向正交，在所述第一导电组和第二导电组的交点处，所述第一导电组和第二导电组之间设置有绝缘光刻胶以使第一导电组和第二导电组彼此绝缘。
一种触控结构的制作方法，包括：
使用上述任一项所述的纳米银线光阻剂，在基片上表面通过光刻工艺形成多个相互绝缘的第一导电组，每一所述第一导电组包括沿第一方向延伸的多个电性连接的第一导电单元；
在所述基片上通过光刻工艺形成绝缘层，所述绝缘层位于相邻两个所述第一导电单元的交汇点上且覆盖所述交汇点；以及
使用上述任一项所述的纳米银线光阻剂，在所述基片上表面通过光刻工艺形成多个相互绝缘的第二导电组，所述多个第一导电组和多个第二导电组呈纵横交错设置，每一所述第二导电组包括沿第二方向延伸的多个电性连接的第二导电单元，相邻两个所述第二导电单元的交汇点位于所述绝缘层之上，第一方向和第二方向交叉。
一种含有触控结构的显示装置，所述显示装置包括显示器、触控结构和盖板，所述触控结构是上述的触控结构。
在一些可选实施例中，所述显示器是液晶显示器、OLED显示器或LED显示器，所述液晶显示器可以包括从下至上依次设置的TFT背板、液晶层、彩色滤光片和偏光片，所述触控结构位于显示器的偏光片和盖板之间并设置在偏光片上或偏光片与盖板之间的绝缘膜上，绝缘膜例如是PET膜，或者所述触控结构设置在彩色滤光片上并位于偏光片和彩色滤光片之间，或者触控结构设置在TFT背板上并位于TFT背板和液晶层之间。
一种含有触控结构的显示装置，包括：
显示器，所述显示器包括偏光片，所述偏光片的上表面设置有多个相互绝缘的第一导电组以及覆盖第一导电组的第一保护层，每一第一导电组沿第一方向延伸且包括多个电性连接的第一导电单元，所述多个第一导电组由上述任一项所述的纳米银线光阻剂形成；
透明绝缘膜，所述透明绝缘膜的下表面设置在所述第一保护层上，所述透明绝缘膜的上表面设置有多个相互绝缘的第二导电组以及覆盖第二导电组的第二保护层，每一第二导电组沿第二方向延伸且包括多个电性连接的第二导电单元，所述多个第一导电组和多个第二导电组呈纵横交错设置，第一方向和第二方向交叉，所述多个第二导电组由上述任一项所述的纳米银线光阻剂形成；
盖板，所述盖板设置在所述第二保护层上。
在一些可选实施例中，所述显示器是液晶显示器、OLED显示器或LED显示器。
相比现有技术，本发明的有益效果至少包括：
1.本发明的纳米银线光阻剂通过采用上述新型结构的分散树脂，该分散树脂可用于纳米银线在多种有机溶剂中的分散润湿，起到替代超分散剂溶剂、提高分散稳定性的作用，使纳米银线光阻剂具有优异的分散性和稳定性，良好的流动性和高的光透过率，并且粘度低、涂布性能良好，得到的纳米银线光阻剂的粘度低于30mPa.s，23℃/50rpm，流变学r值在0.95～1.03之间，展现良好的可涂布性。
2.在制作触摸屏传感器集成一体化时，上述纳米银线光阻剂在黄光制程下可制作10μm以下精细透明导电线条，其方块电阻在20-100欧姆范围，可以实现大尺寸电容式触摸屏的制造，可以替代ITO金属网格电容材料制作各类透明触控线路，尤其在柔性触摸显示方面克服了ITO不耐弯曲的缺点，以及本发明所述的纳米银线光阻剂可以实现黄光制程工艺并直接刻蚀出相应的各类透明导电图型，可以克服ITO或金属网格镀膜蚀刻制作透明电极以及传统水系纳米银线墨水涂布加激光雕刻工艺制作透明电极的工艺不良及复杂过程等缺陷。
3.本发明所述的纳米银线光阻剂可以实现黄光制程工艺直接在氮化镓半导体上进行电极布线，避免了之前的镀膜ITO和蚀刻或激光雕刻等高温、强酸等剧烈理化条件带来的风险，从而提高了Micro-LED显示器的可制造性，同时对工艺流程的环保要求做出贡献。
4.利用本发明的纳米银线光阻剂在偏光片等基膜上光刻制作触控线路，可以获得这种可用于显示触控传感器集成一体化的触摸屏。
5.利用本发明的触摸控件，能够制造将触控传感器集成在显示器上表面的偏光片膜层 上而得到的显示器。
附图说明
图1为采用本发明实施例6的纳米银线光阻剂制造的“菱形”式单层触摸屏用触控电容图型的局部放大图。
图2为本发明实施例的触控结构的示意图。
图3为本发明一个实施例的显示装置的截面示意图；
图4为本发明另一个实施例的显示装置的截面示意图；
图5为本发明另一个实施例的显示装置的截面示意图；其中，101表示显示器，102表示显示器上表面的偏光片，103表示x和y方向“搭桥”式纳米银线光阻剂透明导电图型层，104表示OCA贴合胶层，105表示盖板层。
图6为本发明另一个实施例的显示装置的截面示意图；201表示显示器，202表示带有y方向纳米银线光阻剂透明导电图型层的偏光片，203表示OCA贴合胶层，204表示带有x方向纳米银线光阻剂透明导电图型层的PET膜片，205表示OCA贴合胶层，206表示盖板层。
具体实施方式
以下对本发明的具体实施方式进行描述，但是需要说明的是，在不相冲突的前提下，以下描述的各个实施方式/实施例之间或各个技术特征之间可以任意组合形成新的实施方式/实施例。
实施例1-实施例5是本发明所述的分散树脂的制备方法，在下述实施例中所涉及的试剂均可以通过市场购买方式获得。
实施例1
一种分散树脂，其制备方法如下：
1)低聚物合成：由2-丙烯酸-2羟基-3-苯氧基丙酯15g与甲基丙烯酸4.47g、苯乙烯5.41g；自由基引发剂偶氮二异丁腈0.5g；链转移剂α-甲基苯乙烯线性二聚体0.9g；加入到溶剂丙二醇二甲醚60g当中；在氮气气氛下，加热至90℃，在300rpm下搅拌4Hr，进行自由基反应合成低聚物中间体Z-1，经表征，低聚物中间体Z-1的Mw值为5000-10000；Pd值为2.5以内；粘度<5000cps；
2)产物合成：将30g通式(3)的化合物3-1(其中X为Br)与步骤1)得到低聚物中间体Z-1和0.08g四甲基胍催化剂一起投入三口瓶中；再加入60gDMF溶剂，磁子搅拌加热溶解回流2-3Hr之后，保持反应加热温度90℃，350rpm搅拌8Hr，反应结束后，转 入旋转蒸发仪中旋转蒸发完溶剂，重新加入180g的正丁醇，55℃搅拌1Hr，投入到540g石油醚的锥形瓶中，将沉淀物抽滤干燥，即可得到所述通式(1)的分散树脂1-1，经表征，分散树脂1-1的Mw值为16081；Pd值为2.4。
实施例2
一种分散树脂，其制备方法如下：
1)低聚物合成：由2-丙烯酸-2羟基-3-苯氧基丙酯15g与丙烯酸3.74g、苯乙烯5.41g、甲基丙烯酸甲酯5.2g；自由基引发剂偶氮二异戊腈0.58g；链转移剂α-甲基苯乙烯线性二聚体1.05g；加入到溶剂甲苯50g当中；在氮气气氛下，加热至90℃，300rpm下搅拌4Hr，进行自由基反应合成低聚物中间体Z-2，经表征，低聚物中间体Z-2的Mw值为5000-10000；Pd值为2.5以内；粘度<5000cps；
2)产物合成：将36g通式(3)的化合物3-5(其中X为Br)与步骤1)得到低聚物中间体Z-2一起投入四口瓶中；再加入60g乙腈溶剂，将0.08gKI催化剂溶解到20g乙腈中装入恒压漏斗接到四口瓶，30min滴加完；同时磁子搅拌加热溶解回流4-5Hr之后，保持反应加热温度95℃，350rpm搅拌8Hr，反应结束后，转入旋转蒸发仪中旋转蒸发完溶剂，重新加入180g的正丁醇，55℃搅拌1Hr，投入到540g石油醚的锥形瓶中，将沉淀物抽滤干燥，即可得到所述通式(1)的分散树脂1-2，经表征，分散树脂1-2的Mw值为20350；Pd值为2.3)。
实施例3
一种分散树脂，其制备方法如下：
1)低聚物合成：由2-丙烯酸-2羟基-3-苯氧基丙酯15g与甲基丙烯酸4.47g、甲基丙烯酸甲酯5.2g、甲基丙烯酸苄酯7.4g；自由基引发剂偶氮二异丁腈0.6g；链转移剂α-甲基苯乙烯线性二聚体1.05g；加入到溶剂乙酸乙酯60g当中；在氮气气氛下，加热至80℃，在300rpm下搅拌4Hr，进行自由基反应合成低聚物中间体Z-3，经表征，低聚物中间体Z-3的Mw值为5000-10000；Pd值为2.5以内；粘度<5000cps；
2)产物合成：将40g通式(3)的化合物3-8(其中X为I)与步骤1)得到低聚物中间体低聚物Z-3一起投入四口瓶中；再加入80g乙腈溶剂，将0.08gKI催化剂溶解到20g乙腈中装入恒压漏斗接到四口瓶，30min滴加完；同时磁子搅拌加热溶解回流4-5Hr之后，保持反应加热温度90℃，350rpm搅拌8Hr，反应结束后，转入旋转蒸发仪中旋转蒸发完溶剂，重新加入180g的正丁醇，55℃搅拌1Hr，投入到540g石油醚的锥形瓶中，将沉淀物抽滤干燥，即可得到所述通式(1)的分散树脂1-3，经表征，分散树脂1-3的Mw值为 17168；Pd值为1.8。
实施例4
一种分散树脂，其制备方法如下：
1)低聚物合成：由2-丙烯酸-2羟基-3-苯氧基丙酯15g与丙烯酸3.74g、苯乙烯5.41g、甲基丙烯酸甲酯5.2g、甲基丙烯酸苄酯7.4g；加入到溶剂乙酸乙酯80g当中；自由基引发剂偶氮二异戊腈0.8g和链转移剂α-甲基苯乙烯线性二聚体1.05g恒压漏斗10g乙酸乙酯30min滴加；在氮气气氛下，加热至90℃，300rpm下搅拌4Hr，进行自由基反应合成低聚物中间体Z-4，经表征，低聚物中间体Z-4的Mw值为5000-10000；Pd值为2.5以内；粘度<5000cps；
2)产物合成：将42g通式(3)的化合物3-9(其中X为I)与步骤1)得到低聚物中间体Z-4一起投入四口瓶中；再加入80gDMF溶剂，将0.08g三乙胺催化剂溶解到20gDMF中装入恒压漏斗接到四口瓶，30min滴加完；同时磁子搅拌加热溶解回流4-5Hr之后，保持反应加热温度90℃，350rpm搅拌8Hr，反应结束后，转入旋转蒸发仪中旋转蒸发完溶剂，重新加入200g的正丁醇，55℃搅拌1Hr，投入到600g石油醚的锥形瓶中，将沉淀物抽滤干燥，即可得到所述通式(1)的分散树脂1-4，经表征，分散树脂1-4的Mw值为16115；Pd值为2.2。
实施例5
一种分散树脂，其制备方法如下：
1)低聚物合成：由2-丙烯酸-2羟基-3-苯氧基丙酯15g与甲基丙烯酸4.47g、苯乙烯5.41g、甲基丙烯酸异冰片酯11.55g；自由基引发剂偶氮二异丁腈0.8g；链转移剂α-甲基苯乙烯线性二聚体1.05g；加入到溶剂乙酸乙酯65g当中；在氮气气氛下，加热至90℃，在300rpm下搅拌4Hr，进行自由基反应合成低聚物中间体Z-5，经表征，低聚物中间体Z-5的Mw值为5000-10000；Pd值为2.5以内；粘度<5000cps；
2)产物合成：将40g通式(3)的化合物3-11(其中X为Br)与步骤1)得到低聚物中间体Z-5一起投入四口瓶中；再加入80gDMF溶剂，将0.08gKI催化剂溶解到20g乙腈中装入恒压漏斗接到四口瓶，30min滴加完；同时磁子搅拌加热溶解回流4-5Hr之后，保持反应加热温度95℃，350rpm搅拌8Hr，反应结束后，转入旋转蒸发仪中旋转蒸发完溶剂，重新加入200g的正丁醇，55℃搅拌1Hr，投入到600g石油醚的锥形瓶中，将沉淀物抽滤干燥，即可得到所述通式(1)的分散树脂1-5，经表征，分散树脂1-5的Mw值为19584；Pd值为2.1。
实施例6-12
分别称取以重量份计的以下原料：纳米银线、调色剂、分散树脂、显影树脂、光固化树脂、光引发剂、助剂和有机溶剂。下述表1中的调色剂为浓度1％石墨烯分散浆料，分散树脂为实施例1-5中的分散树脂，显影树脂为甲基丙烯酸-苯乙烯-马来酸酐共聚物，光固化树脂为DPPA，光引发剂为1-羟基环己基苯基甲酮，助剂为氟碳助剂，例如可以使用EFKA3883，有机溶剂A为乙酸丁酯，例如可以使用正丁酯、异丁酯和叔丁酯中的一种或几种的组合，有机溶剂B为3-乙氧基丙酸乙酯。具体配比见表1的纳米银线光阻剂的组分配方。
表1
Figure PCTCN2022101145-appb-000012
表1显示，本发明可以通过光刻工艺的制程制造导电透明图型，且银线分散的效果，对比已有发明进一步提升，没有团聚现象产生。
在制备该纳米银线光阻剂时，先将纳米银线放入部分有机溶剂A中，然后加入调色剂和分散树脂混合制成分散液；再将光固化树脂、光引发剂、显影树脂和助剂溶解在有机溶剂B中，在50-80℃下溶解，然后冷却至25℃后加入上述分散液，并使用机械搅拌或超声 分散或震荡仪或辊摇机等设备之一或几种联用使其充分混合，而后净化灌装，0-5℃保存。
采用上述实施例6-12中的纳米银线光阻剂和OC光阻剂制造的“菱形”式单层触摸屏用触控电容图型，如图1所示，图1中的线宽线距比：L/S为30μm，对其性能参数分析比较，检测结果见表2。
表2
Figure PCTCN2022101145-appb-000013
注：△表示线条未脱落，但对位贴片标记(Marker)有脱落○表示线条和Marker均未脱落。
根据实施例6-12，本发明可得到高分辨率(高精度)，高透过率，低雾度，与基板的密着性强且表面电阻率小的导电图形。进一步，该类导电图型经FPC绑定IC后通电测试下，耐UV1000Hr以及双85高温高湿500Hr可靠性测试后，电阻值仍保持不衰减；对比传统纳米银线材料所制造的触控Sensor，克服了Ag迁移等可靠性不足的现象。
参照图2，本发明还提供一种触控结构，包括多个相互绝缘的第一导电组10和多个相互绝缘的第二导电组20，所述多个第一导电组10和多个第二导电组20呈纵横交错设置，每一第一导电组10沿第一方向延伸且包括多个电性连接的第一导电单元11，每一第一导电组10通过导线向外引出，每一第二导电组20沿第二方向延伸且包括多个电性连接的第二导电单元21，每一第二导电组20通过导线向外引出，第一方向和第二方向交叉，优选正交，所述多个第一导电组10和多个第二导电组20由本发明的纳米银线光阻剂形成。在所述第一导电组10和第二导电组20的交点处，所述第一导电组10和第二导电组20之间设置有绝缘光刻胶以使第一导电组10和第二导电组20彼此绝缘。
上述触控结构的制作方法可以包括：
使用本发明的纳米银线光阻剂，在基片上表面通过光刻工艺形成多个相互绝缘的第一导电组10，基片可以是TFT背板1、彩色滤光片3或偏光片4，每一所述第一导电组10包括沿第一方向延伸的多个电性连接的第一导电单元11。
在所述基片上通过光刻工艺形成绝缘层(未示出)，绝缘层可以通过OC光阻剂形成，所述绝缘层位于相邻两个所述第一导电单元11的交汇点上且覆盖所述交汇点。
使用本发明的纳米银线光阻剂，在所述基片上表面通过光刻工艺形成多个相互绝缘的第二导电组20，所述多个第一导电组10和多个第二导电组20呈纵横交错设置，每一所述第二导电组20包括沿第二方向延伸的多个电性连接的第二导电单元21，相邻两个所述第二导电单元21的交汇点位于所述绝缘层之上，第一方向和第二方向交叉优选正交。
参照图3，本发明还提供一种含有触控结构的显示装置，所述显示装置包括显示器、触控结构和盖板5，所述触控结构是上述的触控结构，显示器可以是液晶显示器、OLED显示器或LED显示器。
在一种实施方式中，参照图5，显示装置具体包括显示器101、显示器101上表面的偏光片102、偏光片102上的x和y方向“搭桥”式纳米银线光阻剂透明导电图型层103、导电图型层103上的OCA贴合胶层104和盖板层105，x和y方向可以垂直。
在另一种实施方式中，参照图6，显示装置具体包括显示器201、显示器201上表面的带有y方向纳米银线光阻剂透明导电图型层的偏光片202、OCA贴合胶层203、带有x方向纳米银线光阻剂透明导电图型层的PET膜片204、PET膜片204上的OCA贴合胶层205和盖板层206，x和y方向可以垂直。
其中，当显示器是液晶显示器时，显示装置可以是In-Cell式、On-Cell式或类OGS式显示装置。
具体地，所述液晶显示器包括从下至上依次设置的TFT背板1、液晶层2、彩色滤光片3和偏光片4，所述触控结构设置在偏光片4上并位于偏光片4和盖板5之间以形成类OGS式显示装置，或者所述触控结构设置在彩色滤光片3上并位于偏光片4和彩色滤光片3之间以形成On-Cell式显示装置，或者触控结构设置在TFT背板1上并位于TFT背板1和液晶层2之间以形成In-Cell式显示装置。
参照图4，本发明还提供另一种含有触控结构的显示装置，包括：显示器、透明绝缘膜6和盖板5。
显示器是液晶显示器、OLED显示器或LED显示器，所述显示器包括偏光片4，所述 偏光片4的上表面设置有多个相互绝缘的第一导电组10以及覆盖第一导电组10的第一保护层(未示出)，每一第一导电组10沿第一方向延伸且包括多个电性连接的第一导电单元11，所述多个第一导电组10由本发明的纳米银线光阻剂形成，偏光片4的下表面可采用全贴合工艺设置在彩色滤光片3上。
透明绝缘膜6可以是PET膜，所述透明绝缘膜6的下表面设置在所述第一保护层上，所述透明绝缘膜6的上表面设置有多个相互绝缘的第二导电组20以及覆盖第二导电组20的第二保护层(未示出)，每一第二导电组20沿第二方向延伸且包括多个电性连接的第二导电单元21，所述多个第一导电组10和多个第二导电组20呈纵横交错设置，第一方向和第二方向交叉，所述多个第二导电组20由本发明的纳米银线光阻剂形成。所述盖板5设置在所述第二保护层上，可采用全贴合工艺完成。此时，触控结构可以设置于透明绝缘膜6上，透明绝缘膜6可以是PET膜。
实施例13
一种根据所述的纳米银线光阻剂在偏光片上表面制造类OGS式双层透明导电层图型触控结构的方法，采用以下步骤制备而成：
1)基片处理：将裁切好尺寸的偏光片(偏光片作为基片)通过真空附着固定，使基片水平铺展在操作台上；
2)制作纳米银线光阻剂导电“搭桥”图型层：依次按照以下步骤进行处理：
2.1)涂布：采用slit方式在所述基片上涂布第一层所述纳米银线光阻剂；
2.2)前烘：涂布后的基片于60-80℃下烘烤2-4min；
2.3)曝光：加掩膜曝光在基片上形成一层厚度为0.08-0.4μm，10-30μm线宽的距形透明掩膜“搭桥”图型，能量50-300mj/cm 2；
2.4)显影：在0.05％KOH中显影1-5min；定义矩形透明导电“搭桥”图型的宽为x方向，长为y方向；
2.5)后烘：80-140℃下烘烤15-30min；
3)制作绝缘光阻“搭桥”图型层，在步骤2)的导电“搭桥”图型层上采用slit方式涂布第一层低温OC光阻剂，然后依次进行前烘、曝光、显影和后烘，处理方法同上述步骤2)；最后形成一层厚度为1-1.2μm的透明绝缘矩形图型，并且在x方向上绝缘光阻“搭桥”图型层完全遮盖导电“搭桥”图型层，在y方向上导电“搭桥”图型层的两端完全从绝缘光阻“搭桥”图型层探出；
4)制作纳米银线光阻“菱形”电极层：在步骤3)的基片上Slit涂布第二层所述纳米 银线光阻剂，再依次经过前烘、曝光、显影、后烘步骤形成厚度为0.04-0.4μm，线宽为30-100μm的“菱形”电极层，使在x方向上经过绝缘光阻“搭桥”顶部的“菱形”电极层连续导通，在y方向上经过绝缘光阻“搭桥”顶部的“菱形”电极层被光刻显影隔断；所述前烘、曝光、显影和后烘的处理方法同上述步骤2)；
5)制作封装保护层：在步骤4)的基片上Slit涂布第二层所述低温OC光阻剂，形成一层厚度为0.3-1μm的透明耐候保护层，并且在边缘可留出连接IC的FPC排线位置；再依次经过前烘、曝光、显影和后烘，上述处理方法同步骤2)。
实施例14
一种采用所述的纳米银线光阻剂制造On-Cell式触摸结构的方法，顺次包括以下步骤：
1)CF基片(彩色滤光片)处理：在CF基片的彩色像素层表面涂布厚度为1μm的保护层，之后该面采用真空附着固定，使CF基片水平铺展在操作台上；
2)制作纳米银线光阻导电“搭桥”图型层：依次按照以下步骤进行处理：
2-1)在步骤a中的CF基片彩色像素层的另一面涂布第一层所述纳米银线光阻剂，真空-0.1MPa；
2-2)前烘：涂布后的基片于80-120℃下烘烤2min；
2-3)曝光：加掩膜曝光在基片上形成一层厚度为0.08-0.4μm的矩形透明导电“搭桥”图型，能量100-300mj/cm 2；
2-4)显影：在0.38％TMAH中显影1min；定义矩形透明导电“搭桥”图型的宽为x方向，长为y方向；
2-5)后烘：180℃下烘烤30min；
3)制作绝缘光阻“搭桥”图型层：在步骤2)的导电“搭桥”图型上涂布第一层OC光阻剂，然后依次进行前烘、曝光、显影和后烘，处理方法同上述步骤2)；最后形成一层厚度为0.5-1.2μm的透明绝缘矩形图型，并且在x方向上绝缘光阻“搭桥”要完全遮盖导电“搭桥”，在y方向上导电“搭桥”的两端完全从绝缘光阻“搭桥”探出，真空-0.1MPa；
4)制作纳米银线光阻“菱形”电极层：在步骤3)的基片上涂布第二层所述纳米银线光阻剂，依次经过真空、前烘、曝光、显影和后烘步骤形成0.08-0.4μm厚度“菱形”电极层，并且在宽度方向上经过绝缘“搭桥”顶部的“菱形”电极层连续导通，在长度方向上经过绝缘“搭桥”顶部的“菱形”电极层被光刻显影隔断；所述真空、前烘、曝光、显影和后烘的处理方法通步骤b；
5)制作封装保护层：在步骤4)的基片上涂布第二层所述OC光阻剂，再依次经过真空、 前烘、曝光、显影和后烘，形成一层0.3-1μm厚度透明耐热耐候保护层，并且在边缘可留出连接IC的FPC排线位置；所述真空、前烘、曝光、显影和后烘的处理方法同步骤2)。
实施例15
一种采用所述的On-Cell式触摸结构制造Micro-LED透明阳极及显示触摸器件的方法，采用如下两种方式中的任意一种制备：
方式一，包括以下步骤：
1)阳极顶端布线：依次按以下步骤处理：
1.1)涂布：在蓝光Micro-LED的像素表面涂布一层所述纳米银线光阻剂，真空-0.1MPa；
1.2)前烘：涂布后的基片于80-120℃下烘烤2min；
1.3)曝光：加掩膜曝光形成一层顶部厚度为0.1-0.2μm的像素级透明导电图型，然后对位套刻，能量100-300mj/cm 2；
1.4)显影：在0.38％TMAH中显影1min；
1.5)后烘：120-240℃下烘烤30min；
2)制作封装保护层：在步骤1)的阳极布线图型层上涂布一层OC光阻剂，再依次经过真空、前烘、曝光、显影和后烘，形成一层0.3-0.5μm厚度的保护层；所述真空、前烘、曝光、显影和后烘的处理方法同步骤1)；
3)对位贴合On-Cell触摸CF基片：在步骤2)的保护层上制作一层OCA光学胶，将所述On-Cell式触摸器件与该OCA光学胶贴合在一起，从而实现该新型全彩触摸显示器的制造。
方式二，包括以下步骤：
1)阳极矩阵布线：
1.1)涂布：在蓝光Micro-LED的像素矩阵处涂布一层所述纳米银线光阻剂，真空-0.1MPa；
1.2)前烘：涂布后的基片于80-120℃下烘烤2min；
1.3)曝光：加掩膜曝光，在矩阵处形成一层厚度为1-3μm、宽度5-10μm的导电矩阵，然后对位套刻，能量100-300mj/cm 2；
1.4)显影：在0.38％TMAH中显影1min；
1.5)后烘：120-240℃下烘烤30min；
2)制作封装保护层：在步骤1)中的阳极布线图型层上涂布一层OC光阻剂，再依次经过真空、前烘、曝光、显影和后烘，形成一层0.3-0.5μm厚度的保护层；所述真空、前烘、曝光、显影和后烘的处理方法同步骤1)；
3)对位贴合On-Cell触摸CF基片：在步骤2)的保护层上制作一层OCA光学胶，将所述On-Cell式触摸器件与该OCA光学胶贴合在一起，从而实现该新型全彩触摸显示器的制造。
实施例16
一种根据所述的纳米银线光阻剂在偏光片上表面制造单层透明导电层图型，贴合一层表面设有单层透明导电层图型的PET膜的双面触控传感器器件，采用以下步骤制备而成：
1)卷涂工艺处理：将偏光片(偏光片作为基片)卷料上表面通过roll to roll涂布线展开；
2)制作纳米银线光阻剂导电图型层：依次按照以下步骤进行处理：
2.1)涂布：采用roll to roll连续涂布方式在所述基片上涂布一层所述纳米银线光阻剂；
2.2)前烘：于60-80℃下烘道烘烤2-4min；
2.3)曝光：加掩膜曝光在出烘道后形成的一层厚度0.04-0.4μm范围的纳米银线光阻膜上，曝光出掩膜图型，能量50-300mj/cm 2；
2.4)显影：在显影线上，使用0.05％KOH中显影1-5min出图案；定义透明导电图型的宽为x方向，长为y方向；
后烘：80-140℃的烘道条件下烘烤15-20min，收卷；
3)制作封装保护层：在步骤2)的卷料上roll to roll开卷涂布一层低温OC光阻剂，形成一层厚度为0.3-1μm的透明耐候保护层，并且在边缘可留出连接IC的FPC排线位置；再依次经过前烘、曝光、显影、后烘(上述处理方法同步骤2)和裁切；
4)在PET基材上制作纳米银线光阻剂导电图型层：依次按照以下步骤进行处理：
4.1)涂布：采用roll to roll连续涂布方式在PET基材上涂布一层所述纳米银线光阻剂；
4.2)前烘：于60-80℃下烘道烘烤2-4min；
4.3)曝光：加掩膜曝光在出烘道后形成一层厚度0.04-0.4μm范围的纳米银线光阻膜上，曝光出掩膜图型，能量50-300mj/cm 2；
4.4)显影：在显影线上，使用0.05％KOH中显影1-5min出图案；定义透明导电图型的宽为x方向，长为y方向；
后烘：80-140℃的烘道条件下烘烤15-20min，收卷；
5)制作封装保护层：在步骤4)的卷料上roll to roll开卷涂布一层低温OC光阻剂，形成一层厚度为0.3-1μm的透明耐候保护层，并且在边缘可留出连接IC的FPC排线位置；再依次经过前烘、曝光、显影、后烘(上述处理方法同步骤2)和裁切；
6)贴合：将裁切后的偏光片纳米银线光阻图形导电膜与裁切后的PET纳米银线光阻 图形导电膜面对背使用OCA贴合胶对位贴合，同时使用邦定机分别将IC和FPC邦定在两片膜的相应位置。
实施例17
一种根据所述的纳米银线光阻剂在PET基材上表面制造类OGS式双层透明导电层图型触控传感器器件的方法，采用以下步骤制备而成：
1)卷涂工艺处理：将PET基材上表面通过roll to roll涂布线展开；
2)制作纳米银线光阻剂导电图型层：依次按照以下步骤进行处理：
2.1)涂布：采用roll to roll连续涂布方式在所述基材上涂布一层所述纳米银线光阻剂；
2.2)前烘：于60-80℃条件下，烘道烘烤2-4min；
2.3)曝光：加掩膜曝光在出烘道后形成的一层厚度0.04-0.4μm范围的纳米银线光阻膜上曝光出10-30μm线宽的距形掩膜“搭桥”图型，能量50-300mj/cm 2；
2.4)显影：在显影线上，使用0.05％KOH中显影1-5min出图案；定义透明导电图型的宽为x方向，长为y方向；
2.6)后烘：80-140℃的烘道条件下烘烤15-20min，收卷；
3)制作绝缘光阻“搭桥”图型层，在步骤2)的导电“搭桥”图型层上采用roll to roll开卷涂布第一层低温OC光阻剂，然后依次进行前烘、曝光、显影、后烘和收卷，处理方法同上述步骤2)；最后形成一层厚度为1-1.2μm的透明绝缘矩形图型，并且在x方向上绝缘光阻“搭桥”图型层完全遮盖导电“搭桥”图型层，在y方向上导电“搭桥”图型层的两端完全从绝缘光阻“搭桥”图型层探出；
4)制作纳米银线光阻“菱形”电极层：在步骤3)的基材上采用roll to roll开卷涂布第二层所述纳米银线光阻剂，再依次经过前烘、曝光、显影、后烘步骤形成厚度为0.04-0.4μm，线宽为30-100μm的“菱形”电极层，使在x方向上经过绝缘光阻“搭桥”顶部的“菱形”电极层连续导通，在y方向上经过绝缘光阻“搭桥”顶部的“菱形”电极层被光刻显影隔断；所述前烘、曝光、显影、后烘和收卷的处理方法同上述步骤2)；
5)制作封装保护层：在步骤4)的卷料上roll to roll开卷涂布一层低温OC光阻剂，形成一层厚度为0.3-1μm的透明耐候保护层，并且在边缘可留出连接IC的FPC排线位置；再依次经过前烘、曝光、显影、后烘(上述处理方法同步骤2)，之后裁切和绑定IC。
实施例18
对实施例13的触控结构，绑定IC的偏光片上表面带有类OGS式双层透明导电层图型，将偏光片的下表面与显示器的上表面通过贴合工艺而贴合在一起，并且，将所述显示 器的上表面与盖板通过贴合工艺而贴合在一起，盖板覆盖双层透明导电层图型，从而得到显示触控一体化器件。
实施例19
对实施例14的触控结构，绑定IC的偏光片上表面带有单层透明导电层图型面，绑定IC的PET膜上表面带有单层透明导电层图型，将偏光片的下表面与显示器的上表面通过贴合工艺而贴合在一起，将PET下表面与偏光片上表面贴合在一起，将PET上表面与盖板通过贴合工艺而贴合在一起，盖板覆盖PET膜上表面的单层透明导电层图型，从而得到显示触控一体化器件。
对本领域的技术人员来说，可根据以上描述的技术方案以及构思，做出其它各种相应的改变以及形变，而所有的这些改变以及形变都应该属于本发明权利要求的保护范围之内。

Claims (13)

  1. 一种纳米银线光阻剂，其特征在于，包括纳米银线和分散树脂，所述分散树脂由式(1)表示：
    (Z-A) n-R m  (1)，
    其中，在式(1)中，n＝1-5，m＝1-5，且n+m≤6；
    Z表示H，或含有氨基、环氧基、具有1～14个碳原子的烷基、具有3～14个碳原子的环烷基或芳基取代基的丙烯酸类共聚物；
    R表示C、N、CH基团、
    Figure PCTCN2022101145-appb-100001
    或含有2-14个碳原子的直链烷基、2-14个碳原子的脂肪环烷基、3-14个碳原子的芳基和杂芳基中的至少一种；
    A由式(2)表示：
    Figure PCTCN2022101145-appb-100002
    并且在式(2)中，W与Z连接，羧基与R连接，W表示H原子、具有1～14个碳原子的取代或未取代的烷基、具有2～6个碳原子的环氧烷基、具有3～14个碳原子的取代或未取代的芳基和取代或未取代的杂芳基中的至少一种。
  2. 根据权利要求1所述的纳米银线光阻剂，其特征在于，
    n＝1-3，m＝1-3，且n+m≤4，和/或
    Z表示选自由甲基丙烯酸、丙烯酸、丙烯酸苄酯、苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸异冰片酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸三环[5.2.1.02,6]癸-8-基酯、甲基丙烯酸羟乙酯、羟丁基丙烯酸酯、氮苯基马来酰亚胺、马来酸酐、2-丙烯酸-2羟基-3-苯氧基丙酯或季戊四醇丙烯酸酯所组成的组中的一种以上化合物所形成的共聚物，和/或
    W表示H、甲基、乙基、羟基取代的烷基、环氧烷基、苯基、苄基、酚基中的至少一种。
  3. 根据权利要求1或2所述的纳米银线光阻剂，其特征在于，A表示由下列各式所表示的化合物中的至少一种：
    Figure PCTCN2022101145-appb-100003
    Figure PCTCN2022101145-appb-100004
  4. 根据权利要求1所述的纳米银线光阻剂，其特征在于，包含以重量份计的以下原料：纳米银线0.1-10份、调色剂0.05-5份、分散树脂0.1-10份、显影树脂0.3-20份、光固化树脂0.4-40份、光引发剂0.05-0.5份、助剂0.05-1份和有机溶剂300-1000份。
  5. 根据权利要求1所述的纳米银线光阻剂，其特征在于，所述纳米银线的平均线径宽度D 50为10-80nm，所述纳米银线的平均长度D 50为3-60μm。
  6. 根据权利要求4所述的纳米银线光阻剂，其特征在于，所述调色剂的粒径为5-200nm，且所述调色剂选自由肽菁颜料、咔唑类颜料、石墨烯和碳纳米管组成的组中的一种或几种。
  7. 一种触控结构，其特征在于，包括多个相互绝缘的第一导电组和多个相互绝缘的第二导电组，所述多个第一导电组和多个第二导电组呈纵横交错设置，每一第一导电组沿第一方向延伸且包括多个电性连接的第一导电单元，每一第二导电组沿第二方向延伸且包括多个电性连接的第二导电单元，第一方向和第二方向交叉，所述多个第一导电组和多个第二导电组由权利要求1至6任一项所述的纳米银线光阻剂形成。
  8. 根据权利要求7所述的触控结构，其特征在于，
    所述第一方向与所述第二方向正交，在所述第一导电组和第二导电组的交点处，所述第一导电组和第二导电组之间设置有绝缘光刻胶以使第一导电组和第二导电组彼此绝缘。
  9. 一种触控结构的制作方法，其特征在于，包括：
    使用权利要求1至6中任一项所述的纳米银线光阻剂，在基片上表面通过光刻工艺形成多个相互绝缘的第一导电组，每一所述第一导电组包括沿第一方向延伸的多个电性连接的第一导电单元；
    在所述基片上通过光刻工艺形成绝缘层，所述绝缘层位于相邻两个所述第一导电单元的交汇点上且覆盖所述交汇点；以及
    使用权利要求1至6中任一项所述的纳米银线光阻剂，在所述基片上表面通过光刻工艺形成多个相互绝缘的第二导电组，所述多个第一导电组和多个第二导电组呈纵横交错设置，每一所述第二导电组包括沿第二方向延伸的多个电性连接的第二导电单元，相邻两个所述第二导电单元的交汇点位于所述绝缘层之上，第一方向和第二方向交叉。
  10. 一种含有触控结构的显示装置，其特征在于，
    所述显示装置包括显示器、触控结构和盖板，所述触控结构是权利要求7或8所述的触控结构。
  11. 根据权利要求10所述的显示装置，其特征在于，所述显示器是液晶显示器、OLED显示器或LED显示器，所述触控结构位于显示器的偏光片和盖板之间并设置在偏光片上或偏光片与盖板之间的绝缘膜上，或者所述触控结构设置在彩色滤光片上并位于偏光片和彩色滤光片之间，或者触控结构设置在TFT背板上并位于TFT背板和液晶层之间。
  12. 一种含有触控结构的显示装置，其特征在于，包括：
    显示器，所述显示器包括偏光片，所述偏光片的上表面设置有多个相互绝缘的第一导电组以及覆盖第一导电组的第一保护层，每一第一导电组沿第一方向延伸且包括多个电性连接的第一导电单元，所述多个第一导电组由权利要求1至6任一项所述的纳米银线光阻剂形成；
    透明绝缘膜，所述透明绝缘膜的下表面设置在所述第一保护层上，所述透明绝缘膜的上表面设置有多个相互绝缘的第二导电组以及覆盖第二导电组的第二保护层，每一第二导电组沿第二方向延伸且包括多个电性连接的第二导电单元，所述多个第一导电组和多个第二导电组呈纵横交错设置，第一方向和第二方向交叉，所述多个第二导电组由权利要求1至6任一项所述的纳米银线光阻剂形成；
    盖板，所述盖板设置在所述第二保护层上。
  13. 根据权利要求12所述的显示装置，其特征在于，所述显示器是液晶显示器、OLED显示器或LED显示器。
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