Classifications

• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
  • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Definitions

• the present invention relates to a transparent electrode composite.
• the transparent electrode film is defined as a thin film which is transparent to visible light and is electrically conductive, and is used in various fields such as a plasma display panel, a liquid crystal display device, a light emitting diode device, an organic light emitting device, a touch panel, and a solar cell. .
• a method of manufacturing an electrode having a crystal pattern formed by covering a dry film solder resist on a substrate such as a PET film, and proceeding in the order of exposure, development, and etching is widely used.
• dry film solder resist there was a limit that it is difficult to realize a line width of less than 40um. Accordingly, in order to remove the limitation on the implementation of the line width, a photoresist is applied on the conductive substrate, and the transparent electrode film is exposed and developed. The method of preparation was also used.
• the transparent electrode film manufactured as described above forms a predetermined protective layer between the conductive substrate and the photoresist layer, and has a low resistance value while having a high bonding strength that the previously known protective layer has on the conductive substrate and the porter resist layer. It should also have low interfacial resistance between neighboring layers.
• the present invention has a high bonding force between the layers, but also has a low sheet resistance and interfacial resistance, and has a high degree of integration through a simplified step, or It is to provide a transparent electrode composite that can form an ultra-fine pattern. [Measures of problem]
• a transparent electrode composite may be provided.
• a transparent electrode composite according to a specific embodiment of the present invention will be described in detail.
• the present inventors experimented through the sol-gel reaction that the polysiloxane-based polymer layer formed on the transparent electrode layer has high hydrophobicity and can secure high coating property and adhesion even to the photosensitive resin layer without a separate post-treatment process. Confirmed through and completed the invention.
• a sol-gel reaction solution containing a siloxane monomer on the transparent electrode and reacting or drying at a temperature of 50 ° C or more, or 1 CX C or more, it is possible to form a polysiloxane polymer with a hydrophobic surface,
• a polysiloxane-based polymer layer may have a high coating property and adhesion to the photosensitive polymer resin composition. Accordingly, a finer pattern can be easily formed in the process of exposing and developing the photosensitive resin layer formed from the photosensitive polymer resin composition.
• the polysiloxane-based polymer layer may have a contact angle with respect to water of 60 ° or more, or 65 ° to 90 ° .
• the polysiloxane-based polymer layer is coated with a sol-gel reaction solution containing a siloxane monomer on the transparent electrode and 50 ° C or more, or ioo ° c or more, 5 (rc to 2 (xrc).
• the polysiloxane-based polymer layer may be formed by reacting or drying at a temperature of the alkyloxy silane monomer, the amino silane monomer, the vinyl silane monomer, the epoxy silane monomer, the methacryloxy silane monomer, the isocyanate silane monomer, and the like. Consisting of fluorine silane monomer It may comprise one polymer or two or more copolymers selected from the group.
• the polysiloxane-based polymer layer may be tetraethyloxysilane, vinyltrieoxysilane, vinyltrimethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, methacryloxypropyltrimethoxysilane, ⁇ (3,4-epoxycyclonucleosilane) ethyltrimethoxysilane, glycidoxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ - ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxysilane, ⁇ -euraidpropyltriethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, polyethylene oxide modified silane monomer, polymethylethoxysilane,
• the polysiloxane-based polymer layer is 60 to 90 weight of tetraethyloxysilane and vinyl trieoxysilane, vinyl Trimethoxysilane, Vinyltris ( ⁇ -Methoxyethoxy) silane, ⁇ -methacryloxypropyltrimethicsilane, ⁇ - (3,4-epoxycyclonucleosilane) ethyltrimethoxysilane, VII-glycidoxy Propyl trimethoxysilane, mercaptopropyl trimethoxysilane, aminopropyl triethoxysilane, ⁇ - ⁇ -
• the sheet resistance of the polysiloxane-based polymer layer may increase significantly.
• the content of tetraethyloxysilane in the monomer used in the synthesis of the copolymer contained in the polysiloxane-based polymer layer is less than 60% by weight, the sheet resistance of the polysiloxane-based polymer layer may increase significantly.
• the density of the polysiloxane-based polymer layer may be excessively high or surface cracking may occur, and moisture resistance may be greatly reduced.
• the transparent electrode composite includes the above-mentioned polysiloxane-based polymer layer Therefore, high coating property and adhesion can be maintained without additional hydrophobic fixation before forming the photosensitive resin layer, and thus a finer pattern can be formed on the photosensitive resin layer.
• the polysiloxane-based polymer layer may have a thickness of 0.050 to 0.300 zm, or 0.1 to 0.200.
• the polysiloxane-based polymer layer may have a sheet resistance of 80 ⁇ / sq to 400 ⁇ / sq, or 150 ⁇ / sq to 280 ⁇ / sq.
• the transparent electrode layer may include various materials known to be used for the transparent electrode, specifically, a conductive polymer, carbon nanotubes, graphene, silver nanowires (AgNw), copper nanoparticles, and indium tin oxide (Indium) Tin Oxide) and antimony tin oxide may include one or more compounds selected from the group consisting of.
• a conductive polymer specifically, carbon nanotubes, graphene, silver nanowires (AgNw), copper nanoparticles, and indium tin oxide (Indium) Tin Oxide) and antimony tin oxide may include one or more compounds selected from the group consisting of.
• the conductive polymer may be a polymer known to be used for a transparent electrode.
• the conductive polymer may be a polyaniline-based polymer, a polypyrrole-based polymer, a polythiophene-based polymer, and derivatives thereof. It may include, and may specifically use PED0T: PSS [Poly (3, 4- et hy 1 ened i oxy thi ophene): Polystyrene sul fonate].
• the transparent electrode layer may have a thickness of 0.20 // m to 3.00, or 0.30 ⁇ s to 1.0. If the thickness of the transparent electrode layer is too thin, the effective sheet resistance may also be greatly reduced, and the sheet resistance may be uneven. If the thickness of the transparent electrode layer is too thick, transparency or optical characteristics may be degraded.
• the transparent electrode layer may have a sheet resistance of 80 ⁇ / sq to 400 ⁇ / sq, or 150 ⁇ / sq to 280 ⁇ / sq.
• the photosensitive resin layer may be uniformly and firmly bonded on the polysiloxane-based polymer layer, thereby providing a finer pattern on the photosensitive resin layer. Can be formed.
• the photosensitive resin layer may be used a photosensitive resin composition or photoresist composition commonly known, specifically, the photosensitive resin layer is a positive photoresist composition containing an alkali-soluble resin; Or including monomers or multimers and photoinitiators comprising one or more semi-active functional groups Negative photoresist composition; and preferably from positive photoresist composition.
• the photosensitive resin layer is a positive photoresist composition containing an alkali-soluble resin; Or including monomers or multimers and photoinitiators comprising one or more semi-active functional groups Negative photoresist composition; and preferably from positive photoresist composition.
• the photosensitive resin layer may have a thickness of 1 to zm, or 2 // m to 4 / zm. If the thickness of the photosensitive resin layer is too thin, staining or appearance damage may occur on the photosensitive resin layer and / or the polysilonic acid polymer layer during exposure, development, and etching, thereby causing a cloudy appearance. If the thickness of the photosensitive resin layer is too thick, exposure may not be easy and development may not occur sufficiently or mismatch of line width may occur.
• the electrode film may further include a release film layer formed on the photosensitive resin layer.
• the release film layer may be a polymer film or the like, which is commonly used in the transparent electrode film, and specifically, a silicone adhesive film, an acrylic adhesive film, a PE protective film, or the like may be used.
• the electrode film may further include a base film layer formed on one surface of the transparent electrode layer to face the polysiloxane-based polymer layer.
• the transparent electrode layer after the transparent electrode layer is formed on the base film layer, the transparent electrode layer, the polysiloxane-based polymer layer, and the photosensitive resin layer may be sequentially formed to form the transparent electrode composite.
• the base film layer may be formed on the other surface of the transparent electrode layer to form the transparent electrode composite.
• a conventionally known coating method or coating method may be used, and also commonly known pressing methods may be used.
• a conventional coating method used in the art such as spray method, bar coating method, doctor blade method, coating method, dipping method may be applied.
• a transparent electrode composite having high bonding force and low sheet resistance and interfacial resistance between each layer, and having a high integration degree or a micronized pattern can be formed through a simplified step can be provided.
• the transparent electrode composite provides a transparent electrode structure including a photosensitive resin layer which is a photoactive layer, and serves as a buffer of the transparent electrode and the photosensitive resin layer.
• a photosensitive resin layer which is a photoactive layer
• Including a polysiloxane-based polymer layer can be exhibited its unique properties. In particular, high coating properties and adhesion can be maintained without additional hydrophobic fixation prior to coating of the photosensitive resin layer, thereby forming a finer pattern on the photosensitive resin layer.
• FIG. 1 illustrates contact angles of water of the polysiloxane-based polymer layers obtained in Examples 1 and 2 and Comparative Example 1.
• FIG. 1 illustrates contact angles of water of the polysiloxane-based polymer layers obtained in Examples 1 and 2 and Comparative Example 1.
• Figure 2 shows the appearance of the pattern of Example 1 and Comparative Example 1 observed in Experimental Example 2.
• PED0T PSS [Po 1 y (3, 4-et hy 1 ened i oxy thi ophene) Polystyrene sul fonate, solids wt%], IPA (isopropylene alcohol), MeOH (methane) and DMS0 (dimethylsulfoxide) was mixed at a weight ratio of 75: 15: 5: 5, and 500 parts of Dynol 607, a surface regulator, was added to the mixture and stirred.
• the mixture was coated on a PET substrate using a bar coater, followed by hot air drying (110 ° C./60 seconds) to prepare an electrode layer having a thickness of 0.096.
• the sheet resistance of the finally prepared electrode layer was 240Q / sq.
• PED0T PSS [Po 1 (3, 4-et hy 1 ened i oxy thi ophene) Polystyrene sul fonate, solid content 0.35wt%], silver nanowire dispersion (lwt%, water), IPA (isopropylene alcohol) , DI water And EG (ethylene glycol) was mixed in a weight ratio of 28.5: 10: 10: 41.5: 10, and the surface control agent 3M FC-4330 was added to 500ppmw compared to the mixture and stirred.
• TE0S tetraethyloxysilane
• PTMS phenyltrimethoxysilane
• 23.55 g of water, 54.95 g of IPA (isopropylene alcohol) and 1.4 g of acetic acid were mixed and reacted for 3 hours at 70 ° C.
• 100 g of the gel reaction solution (solid content 7.8wt) was prepared and 500 g of the sol-gel reaction solution (solid content 1.56 wt3 ⁇ 4) was prepared by diluting the prepared sol-gel reaction solution and isopropylene alcohol at a weight ratio of 1: 4.
• the sol-gel reaction solution (solid content 1.56 ⁇ %) was coated on the electrode layer obtained in Preparation Example 1 with a thickness of 11.4 kPa using a bar coater, and then dried for 10 minutes at 20 ° C.
• a polysiloxane polymer layer (surface resistance: 260 Q / sq) having a thickness of mi was formed.
• Dongjin Semicam photoresist (Posi tive Type) SJ-631 (10cP, solid content 23 ⁇ %) was applied to the polysiloxane-based polymer layer formed by using a bar coating, and dried at 120T for 1 minute to be about 2.62 thick The photosensitive resin layer was produced.
• Example 2 Dongjin Semicam photoresist (Posi tive Type) SJ-631 (10cP, solid content 23 ⁇ %) was applied to the polysiloxane-based polymer layer formed by using a bar coating, and dried at 120T for 1 minute to be about 2.62 thick The photosensitive resin layer was produced.
• the sol-gel reaction solution (solid content 1.44 ⁇ %) was coated on the electrode layer obtained in Preparation Example 1 with a thickness of 11.43 using a bar coater, and then hot air. After drying at 20 ° C. for 10 minutes under conditions, a polysiloxane-based polymer layer (surface resistance: 265Q / sq) having a thickness of 0.165 was formed.
• Dongjin Semichem photoresist (Positive Type) SJ-631 (10cP, solid content 23 ⁇ ⁇ %) was applied to the polysiloxane-based polymer layer formed by using a bar coating, and dried at a temperature of 12 (C temperature for 1 minute to about 2.62 thick A photosensitive resin layer was prepared.
• the polysiloxane sol-gel reaction solution (solid content 1.44 ⁇ %) prepared in Example 2 was coated on the electrode layer obtained in Preparation Example 2 to a thickness of 11.43 kPa using a bar coater, and then subjected to hot air conditions at 20 ° C. It dried for 10 minutes at and formed the polysiloxane-type polymer layer (surface resistance: 80Q / sq) of 0.165 thickness.
• Dongjin Semichem photoresist (Positive Type) SJ-631 (10cP, solid content 23wt3 ⁇ 4) was applied to the polysiloxane-based polymer layer formed by using a bar coating, dried at 120 ° C for 1 minute to a thickness of about 2.62 / / ⁇ 1 The photosensitive resin layer was produced. Examples 4-6
• the sol-gel reaction solution (solid content 1.4wt%) was coated on the electrode layer obtained in the preparation example using a bar coater at a thickness of 11.4 im, and then dried at a temperature of 20 ° C. for 10 minutes under hot air conditions.
• a polysiloxane polymer layer (surface resistance: 256 Q / sq) having a thickness of 160 was formed.
• Dongjin Semichem Photoresist (Posi tive Type) SJ-631 (10cP, solid content 23wt%) was applied to the polysiloxane-based polymer layer formed by using a bar coating, dried at 120 ° C for 1 minute to about 2.62 / zm
• the photosensitive resin layer of thickness was produced.
• the coating property and adhesion on the basis of whether or not the line width of the pattern is removed in the pattern formation process is represented by 0 when the pattern is maintained and X when removing the pattern shown in Table 1 below, It is described in Figure 2 below.
• the electrode films of Examples 1 to 3 can be more easily and firmly combined with the photosensitive resin layer, including a polysiloxane-based polymer layer having a contact angle of 60 degrees or more, thereby improving coating properties and adhesion.
• the castle can be secured.
• the bonding force between the polysiloxane-based polymer layer and the photosensitive resin layer of the electrode film of Comparative Example 1 was not sufficient, so that the formed pattern did not adhere well or part of the shape was not maintained.

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• 2014
  • 2014-07-08 KR KR1020140085142A patent/KR102287289B1/ko active IP Right Grant
• 2015
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