WO2016136746A1 - Stratifié, panneau tactile et procédé de formation de motifs pour stratifié - Google Patents

Stratifié, panneau tactile et procédé de formation de motifs pour stratifié Download PDF

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Publication number
WO2016136746A1
WO2016136746A1 PCT/JP2016/055269 JP2016055269W WO2016136746A1 WO 2016136746 A1 WO2016136746 A1 WO 2016136746A1 JP 2016055269 W JP2016055269 W JP 2016055269W WO 2016136746 A1 WO2016136746 A1 WO 2016136746A1
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refractive index
metal
high refractive
organic resin
forming
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PCT/JP2016/055269
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English (en)
Japanese (ja)
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和輝 江口
政太郎 大田
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日産化学工業株式会社
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Priority to JP2017502389A priority Critical patent/JP6751271B2/ja
Publication of WO2016136746A1 publication Critical patent/WO2016136746A1/fr

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    • 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

Definitions

  • the present invention relates to a laminate that can be used for, for example, a capacitive touch panel, a touch panel using the laminate, and a method for patterning the laminate.
  • a capacitive substrate is widely used as a preferred method because it can be thinned by using a single substrate.
  • Such a touch panel is incorporated in a display device such as a liquid crystal display device and is used as a display device with a touch panel function capable of detecting a touch position. Since a person who operates the touch panel visually recognizes the display device through the touch panel, a member having excellent light transmission characteristics is used for the transparent electrode. For example, an inorganic material such as ITO (Indium Tin Oxide) is used.
  • ITO Indium Tin Oxide
  • the above-described technique has a problem that the visual phenomenon of the electrode pattern cannot be suppressed depending on the structure of the touch panel. That is, in the touch panel structure in which a cover glass is provided via an adhesive layer, the visibility of the electrode pattern is suppressed, but in the touch panel structure having an air layer between the cover glass, the visibility phenomenon cannot be suppressed. There is.
  • the metal alkoxy layer needs to be patterned by a printing technique such as flexographic printing, but has a problem that it cannot cope with a fine pattern.
  • the present invention has been made in view of the above points, and an object of the present invention is to provide a laminate, a touch panel, and a laminate patterning method capable of reducing deterioration in display properties of a display device due to visual recognition of a transparent electrode pattern. Is to provide.
  • Another object of the present invention is to provide a capacitance formed by forming on the transparent electrode a film that can be formed with high hardness, high adhesion with the transparent electrode, and film formation using printing technology. It is to provide a touch panel of the type.
  • the present invention relates to a transparent substrate, a transparent electrode patterned on the transparent substrate, a high refractive index layer provided so as to cover the transparent electrode, and an organic resin layer provided on the high refractive index layer And the high refractive index layer is patterned by the patterning shape of the organic resin layer.
  • the high refractive index layer preferably has a refractive index of 1.50 to 1.75 and a film thickness of 40 nm to 170 nm.
  • the high refractive index layer is preferably an inorganic metal oxide layer.
  • the high refractive index layer has the following general formula (I) M 1 (OR 1 ) n (I) (In the formula, M 1 represents a metal, R 1 represents a C1-C5 alkyl group, and n represents a valence of M 1. )
  • the organic resin layer is preferably formed of a negative radiation sensitive organic resin.
  • the organic resin layer preferably has a refractive index of 1.45 to 1.65.
  • the organic resin layer preferably has a thickness of 0.5 ⁇ m to 10 ⁇ m.
  • the present invention includes a step of applying a coating solution for forming a high refractive index layer so as to cover a transparent electrode patterned on a transparent substrate, and drying to form a coating film for forming a high refractive index layer, Forming a coating film for forming an organic resin layer on a coating film for forming a refractive index layer, patterning the coating film for forming an organic resin layer to form an organic resin layer, and applying the coating for forming a high refractive index layer And a step of patterning the film in accordance with the pattern shape of the organic resin layer.
  • the coating film for forming the organic resin layer and the coating film for forming the high refractive index layer are patterned with the same developer.
  • the organic resin layer forming coating film is patterned with a developer to form the organic resin layer, and then the high refractive index layer forming coating film is formed through the organic resin layer. It is preferable that the coating film be patterned with a developer different from the patterned developer.
  • the high refractive index layer is preferably an inorganic metal oxide layer having a refractive index of 1.50 to 1.75 and a film thickness of 40 nm to 170 nm.
  • the coating liquid for forming the high refractive index layer has the following general formula (I) M 1 (OR 1 ) n (I) (In the formula, M 1 represents a metal, R 1 represents a C1-C5 alkyl group, and n represents a valence of M 1. )
  • the precipitation inhibitor is preferably at least one selected from the group consisting of N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexylene glycol, and derivatives thereof.
  • the molar ratio of the metal atoms of the metal alkoxide contained in the high refractive index layer-forming coating liquid (M 1), a metal atom of the metal salt and (M 2) is 0.01 ⁇ M 2 / (M 1 + M 2 ) ⁇ 0.7 It is preferable that
  • the metal salt is a group consisting of metal nitrate, metal sulfate, metal acetate, metal chloride, metal sulfamate, metal sulfonate, metal acetoacetate, metal acetylacetonate, and basic salts thereof. It is preferably at least one selected from
  • the present invention also provides a touch panel comprising the above laminate.
  • a laminate in which the transparent electrode pattern is not visually recognized can be provided, and the visibility of the transparent electrode pattern is suppressed even when used for various touch panels and other applications.
  • the laminate of the present invention is provided on a transparent substrate, a transparent electrode patterned on the transparent substrate, a high refractive index layer provided to cover the transparent electrode, and the high refractive index layer.
  • An organic resin layer, and the high refractive index layer is patterned by a patterning shape of the organic resin layer.
  • the laminate of the present invention comprises two refractive index adjusting layers, a high refractive index layer and an organic resin layer, on a transparent electrode.
  • the reason why the display performance of the display device is deteriorated when the transparent electrode pattern is visually recognized is that the refractive index of the transparent electrode is different from the refractive index of the substrate.
  • the transparent electrode is usually made of ITO (Indium Tin Oxide), which is an inorganic metal oxide.
  • ITO Indium Tin Oxide
  • the refractive index of ITO is about 1.8 to 2.1. Is about 1.5, which is very different from the refractive index of ITO because of the difference in the light reflection characteristics between the region where the transparent electrode is formed and the region where the transparent electrode is not formed. That is, the interfacial reflection characteristics with interference differ between the region where the transparent electrode is formed and the region where the transparent electrode is not formed, which results in conspicuous electrode patterns in the screen display.
  • the present inventor is controlled so that the refractive index and the film thickness are within a desired range on the transparent electrode arranged on the substrate.
  • the present inventors have found that it is effective to provide a high refractive index layer and an organic resin layer having a predetermined refractive index superimposed thereon.
  • By providing such a two-layer adjustment layer it is possible to suppress the phenomenon that an unintended electrode pattern is visually recognized in any touch panel structure, and the visibility of the transparent electrode in the laminate itself can be reduced. Since it can suppress, it discovered that a laminated body can be easily applied also to uses other than a touch panel.
  • an insulating film should not be arranged on the wiring part of the frame part of the touch panel, but in recent years, fine patterning is required due to the narrowing of the frame of the element.
  • Fine patterning is difficult. Therefore, in forming a film, it is necessary to use a photolithographic technique having a complicated process, but even if the high refractive index layer cannot be patterned by the photolithographic technique, by patterning the two layers together, Patterning by photolithography technology becomes possible.
  • the high refractive index layer preferably has a refractive index of 1.50 to 1.75 and a film thickness of 40 nm to 170 nm.
  • the high refractive index layer is preferably an inorganic metal oxide layer that is excellent in the function of protecting the transparent electrode, specifically, excellent in mechanical strength and capable of protecting the transparent electrode from multiple pressings with a finger or the like. Particularly preferred is a predetermined inorganic metal oxide layer described below.
  • the organic resin layer preferably has a refractive index of 1.45 to 1.65.
  • the organic resin layer is preferably directly patterned by photolithography, that is, formed from a radiation-sensitive organic resin.
  • the high refractive index layer can be patterned simultaneously with the patterning of the organic resin layer, and the high refractive index layer can be patterned through the patterned organic resin layer. You can also.
  • FIG. 1A and 1B are configuration diagrams of a touch panel according to a first embodiment of the present embodiment, in which FIG. 1A is a plan view, FIG. 1B is a cross-sectional view along line AA ′ in FIG. It is a BB 'sectional view taken on the line (a).
  • the touch panel 1 includes a transparent substrate 2, a first transparent electrode 3 for detecting coordinates in the X direction, and a second transparent electrode 4 for detecting coordinates in the Y direction.
  • the first transparent electrode 3 and the second transparent electrode 4 are formed from the same layer provided on the same surface of the substrate 2.
  • the substrate 2 is made of a transparent material such as glass, acrylic resin, polyester resin, polyethylene terephthalate resin, polycarbonate resin, polyvinylidene chloride resin, polymethyl methacrylate resin, triacetyl cellulose resin, and polyethylene naphthalate resin.
  • a transparent material such as glass, acrylic resin, polyester resin, polyethylene terephthalate resin, polycarbonate resin, polyvinylidene chloride resin, polymethyl methacrylate resin, triacetyl cellulose resin, and polyethylene naphthalate resin.
  • the thickness of the substrate 2 is, for example, about 0.1 mm to 2 mm when glass is used, and is about 10 ⁇ m to 2000 ⁇ m, for example, when a resin film is used.
  • the first transparent electrode 3 and the second transparent electrode 4 are formed at positions corresponding to the operation surface of the touch panel 1.
  • the first transparent electrode 3 is provided separately in a plurality of regions along the X direction
  • the second transparent electrode 4 is provided separately in a plurality of regions along the Y direction. Yes. With such a structure, the accuracy of touch position detection can be increased.
  • each of the first transparent electrode 3 and the second transparent electrode 4 includes a plurality of pad portions 21, and each pad portion 21 is isolated in a planar manner, and each pad portion It arrange
  • the pad part 21 can be made into polygonal shapes, such as a rhombus, a rectangle, and a hexagon, for example, These are arrange
  • the first transparent electrode 3 and the second transparent electrode 4 are formed using a transparent electrode material having a high transmittance for at least visible light and having conductivity.
  • a transparent electrode material having conductivity include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and ZnO (Zinc Oxide).
  • ITO Indium Tin Oxide
  • IZO Indium Zinc Oxide
  • ZnO Zinc Oxide
  • the thickness is preferably 10 nm to 200 nm so as to ensure sufficient conductivity.
  • the first transparent electrode 3 and the second transparent electrode 4 are formed as follows.
  • the transparent conductive film is formed by a method selected in consideration of the material of the substrate 2 as a base from sputtering, vacuum deposition, ion plating, spray, dipping, or CVD (Chemical Vapor Deposition). Is deposited.
  • the transparent conductive film is patterned using a photolithography technique.
  • a desired pattern may be formed by a printing method using a paint in which a conductive filler made of the above material is dispersed in an organic solvent.
  • the first transparent electrode 3 and the second transparent electrode 4 are formed on the same surface of the substrate 2 and form the same layer. For this reason, the 1st transparent electrode 3 and the 2nd transparent electrode 4 cross
  • one of the first transparent electrode and the second transparent electrode is divided so as not to contact the other. That is, as shown in FIG. 1B, the second transparent electrode 4 is connected to any of the plurality of intersecting portions 18, but the first transparent electrode 3 is divided. And in order to connect the parting part of the 1st transparent electrode 3, the bridging electrode 20 is provided and the interlayer insulation film 19 which consists of an insulating substance between the bridging electrode 20 and the 2nd transparent electrode 4 is provided. Is provided.
  • a light transmissive interlayer insulating film 19 is formed on the second transparent electrode 4 at the intersection 18.
  • an inorganic material such as SiO 2 or an organic material such as a photosensitive acrylic resin can be used.
  • SiO 2 for example, a structure in which an SiO 2 film is formed only on the second transparent electrode 4 at the intersection 18 by a sputtering method using a mask can be used.
  • a photosensitive acrylic resin the same structure can be formed using the photolithographic method.
  • a bridging electrode 20 is provided in the upper layer of the interlayer insulating film 19.
  • the bridging electrode 20 is for electrically connecting the first transparent electrodes 3 separated by the intersecting portion 18 and is formed of a light transmissive material. By providing the bridging electrode 20, the first transparent electrode 3 can be electrically connected in the Y direction.
  • the first transparent electrode 3 and the second transparent electrode 4 have a shape in which a plurality of rhombus pad portions 21 are arranged vertically or horizontally.
  • the connection portion located at the intersecting portion 18 has a shape narrower than the rhomboid pad portion 21 of the second transparent electrode 4.
  • the bridging electrode 20 is also formed in a strip shape having a narrower width than the diamond-shaped pad portion 21.
  • the first transparent electrode 3 and the second transparent electrode 4 are placed on the first transparent electrode 3 and the second transparent electrode 4 (that is, the first transparent electrode 3 and the second transparent electrode 4 are disposed).
  • a high refractive index layer 5 and an organic resin layer 6 are formed, and a laminate 7 is formed. And the formation area and non-formation area
  • the high refractive index layer 5 has a high hardness and is excellent in adhesion with the first transparent electrode 3 and the second transparent electrode 4.
  • the organic resin layer 6 is excellent in adhesion with the high refractive index layer 5.
  • the high refractive index layer 5 may be made of any organic material, inorganic material, and organic-inorganic hybrid material as long as it has the predetermined refractive index described above, but has excellent mechanical strength and can protect the transparent electrode. It is preferably made of an inorganic material or an organic-inorganic hybrid material because of its excellent function and adhesion to the transparent electrode. Of these, inorganic metal oxides are preferred as the inorganic material.
  • the high refractive index layer 5 is formed by hydrolyzing and condensing a metal alkoxide in an organic solvent in the presence of a metal salt (for example, an aluminum salt) and further adding a precipitation inhibitor.
  • a metal salt for example, an aluminum salt
  • a coating solution is used. Details of the coating solution for forming the high refractive index layer will be described later.
  • the refractive index and the film thickness of the high refractive index layer 5 are selected so that the electrode patterns of the first transparent electrode 3 and the second transparent electrode 4 are not visible.
  • the refractive index of the high refractive index layer 5 is preferably in the range of 1.50 to 1.75, more preferably in the range of 1.54 to 1.70.
  • the film thickness is preferably in the range of 40 nm to 170 nm.
  • the film thickness is more preferably in the range of 60 nm to 150 nm.
  • the film thickness is further preferably in the range of 40 nm to 170 nm.
  • the high refractive index layer 5 is selected from metal oxide layers that are insulative and have high visible light transparency so that the first transparent electrode 3 and the second transparent electrode 4 do not conduct.
  • the high refractive index layer 5 is formed from a coating composition containing silicon alkoxide and titanium alkoxide, and has a refractive index of 1.60 and a film thickness of 80 nm.
  • the organic resin layer 6 is provided on the high refractive index layer 5, and the patterning shape of the high refractive index layer 5 matches the patterning shape of the organic resin layer 6. That is, the high refractive index layer 5 is separately patterned simultaneously with the patterning of the organic resin layer 6 or using the organic resin layer 6 as a mask.
  • the organic resin layer 6 may be patterned by providing a resist layer thereon, but is preferably made of a radiation-sensitive organic resin.
  • Radiation-sensitive organic resins use ultraviolet rays, specifically g-rays, i-rays, KrF excimer laser light, ArF excimer laser light, etc., as well as electron beams, X-rays, EUV light (extreme ultraviolet rays), etc.
  • the material can be patterned by the conventional lithography technique and may be a negative type or a positive type, but a negative type is preferable.
  • the organic resin layer 6 preferably has a refractive index of 1.45 to 1.65, more preferably 1.47 to 1.61. By having such a refractive index, the visibility of the transparent conductive film in the laminate is suppressed, and if the visibility in the laminate is suppressed, a cover glass is provided via an adhesive. Even with a touch panel or a touch panel in which a cover glass is provided via an air layer, the effect of suppressing the visibility of the transparent electrode can be obtained.
  • the organic resin layer 6 preferably has a film thickness of 0.5 ⁇ m to 10 ⁇ m, more preferably 0.5 ⁇ m to 5 ⁇ m.
  • the radiation-sensitive organic resin is a polymer containing an organic group soluble in alkali and a polymerizable group.
  • the polymer include polymers obtained by copolymerization using monomers having an unsaturated double bond such as acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, and styrene.
  • the alkali-soluble organic group include an organic group having a carboxyl group, a phenolic hydroxyl group, an acid anhydride group, and a maleimide group.
  • Examples of the organic group having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyl. Phenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, 4-vinylbenzoic acid and the like.
  • Examples of the organic group having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like.
  • Examples of the organic group having an acid anhydride group include maleic anhydride and itaconic anhydride.
  • Examples of the organic group having a maleimide group include maleimide.
  • polymerizable group examples include, but are not limited to, an acrylate group, a methacrylate group, a vinyl group, and an allyl group.
  • specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, penta Erythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane te
  • Photopolymerization initiator If the photoinitiator contained in a photosensitive polymer in the coating liquid for radiation sensitive organic resins generate
  • Specific examples include aromatic ketones such as benzophenone, Michler ketone, 4,4′-bisdiethylaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrene, benzoin methyl ether, benzoin ethyl ether, Benzoin ethers such as benzoinphenyl ether, benzoin such as methylbenzoin and ethylbenzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di ( m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl
  • the above photopolymerization initiator can be easily obtained as a commercial product. Specific examples thereof include IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 1300, IRGACURE 819, IRGACURE 819DW, IRGACURE 1880, IRGACURE 1870, DAROCURE TPO, DAROCURE 4265, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE 250, and above (made by BASF) RE 2-EAQ (Nippon Kayaku Co., Ltd.), TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-106, TAZ-107, TAZ-108, TAZ-110, TAZ-113, TAZ-114, TAZ-118, TAZ-122, TAZ-123, TAZ-140, TAZ-204 (manufactured by Midori Chemical Co.,
  • the touch panel 1 has a cover glass 10 superimposed on an adhesive layer 9 using an acrylic photocurable resin or the like on a surface of the laminate on which the first transparent electrode 3 or the like is formed. Consists of.
  • the adhesive layer 9 is provided on the organic resin layer 6.
  • the touch panel 1 is used for a display device, for example, and the display device includes the touch panel 1 and a display panel, and may have a backlight as necessary. Although details are omitted in FIG. 1, the display panel can have the same configuration as a known display device.
  • the display panel in the case of a liquid crystal display device, can have a structure in which a liquid crystal layer is sandwiched between two transparent substrates.
  • a polarizing plate can be provided on the side of each transparent substrate opposite to the side in contact with the liquid crystal layer.
  • a segment electrode or a common electrode can be formed on each transparent substrate in order to control the state of the liquid crystal.
  • the liquid crystal layer is sealed with each transparent substrate and a sealing material.
  • terminals are provided at end portions of the first transparent electrode 3 and the second transparent electrode 4 of the laminated body 7, and a plurality of terminals are provided from the terminals.
  • Lead-out wiring 11 is drawn out.
  • the lead-out wiring 11 can be an opaque metal wiring using silver, aluminum, chromium, copper, molybdenum, or an alloy containing these metals such as Mo—Nb (molybdenum-niobium) alloy.
  • the lead-out wiring 11 is connected to a control circuit (not shown) that detects voltage application and a touch position to the first transparent electrode 3 and the second transparent electrode 4.
  • a voltage is sequentially applied to the plurality of first transparent electrodes 3 and the second transparent electrodes 4 to give an electric charge.
  • a capacitor is formed by capacitive coupling between the fingertip and the first transparent electrode 3 and the second transparent electrode 4. Therefore, it is possible to detect which part of the finger touched by capturing the change in the charge at the contact position of the fingertip.
  • the touch panel 1 can also selectively apply a voltage to either the first transparent electrode 3 or the second transparent electrode 4 under the control of a control circuit (not shown).
  • a control circuit not shown
  • an electric field is formed on the transparent electrode to which a voltage is applied, and when a finger or the like touches in this state, the contact position is grounded via the capacitance of the human body.
  • a change in resistance value occurs between the terminal (not shown) of the target first transparent electrode 3 or second transparent electrode 4 and the contact position. Since this resistance value is proportional to the distance between the contact position and the terminal of the first transparent electrode 3 or the second transparent electrode 4 as a target, the contact position and the first transparent electrode 3 or the first transparent electrode 3 as a target.
  • the coordinates of the contact position can be obtained by the control circuit detecting the current value flowing between the two transparent electrodes 4.
  • the conspicuous electrode pattern on the operation surface is suppressed by the effect of the high refractive index layer 5 provided on the first and second transparent electrodes 3 and 4.
  • 2 (a) to 2 (f) are process cross-sectional views illustrating a manufacturing method of a touch panel as a first example of the present embodiment.
  • a transparent substrate 2 such as a glass substrate is prepared.
  • the substrate 2 is cut into a desired shape and washed as necessary. Further, an intermediate layer such as SiOx, SiNx, or SiON may be formed between the substrate 2 and the transparent conductive film.
  • a transparent conductive film is formed on one surface of the substrate 2.
  • the transparent conductive film is, for example, ITO, and is formed to a thickness of 10 nm to 200 nm using a sputtering method, a vacuum evaporation method, or the like.
  • the transparent conductive film is etched in a state where an etching mask made of a photosensitive resin or the like is formed on the upper layer side of the transparent conductive film, and the first transparent electrode 3 and the second transparent electrode 4 are formed by patterning.
  • an etching mask made of a photosensitive resin or the like is formed on the upper layer side of the transparent conductive film, and the first transparent electrode 3 and the second transparent electrode 4 are formed by patterning.
  • the second transparent electrode 4 is connected via a connection portion, but the first transparent electrode 3 is divided.
  • the interlayer insulating film 19 and the bridging electrode 20 are formed, but this step is omitted.
  • photosensitive resin for forming the interlayer insulation film 19 what has transparency and heat resistance is used.
  • an acrylic resin can be used.
  • the interlayer insulating film 19 is formed using SiO 2 , the same structure can be obtained by sputtering using a mask.
  • the bridging electrode 20 is formed of a transparent electrode such as an ITO film so as to connect the divided portion of the first transparent electrode 3 to the upper layer of the interlayer insulating film 19.
  • the above-described lead-out wiring 11 is formed using silver ink or the like in a later process. However, when the transparent conductive film is etched in the above step, the transparent conductive film is left along the outer peripheral edges of the first transparent electrode 3 and the second transparent electrode 4 to form the lead-out wiring 11. Is possible.
  • a coating solution for forming a high refractive index layer is applied on the first transparent electrode 3 and the second transparent electrode 4.
  • the coating liquid for forming a high refractive index layer will be described later, this is coated and then dried to obtain a coating film 15 for forming a high refractive index layer.
  • the coating film 15 for forming a high refractive index layer here is dried to such an extent that it retains the solubility in a developer used in the development step described later.
  • an organic resin layer forming coating solution 16 is formed on the high refractive index layer forming coating film 15 to form an organic resin layer forming coating film 16.
  • a coating solution containing a negative photosensitive organic resin is used as the coating solution for forming the organic resin layer.
  • ultraviolet rays having a predetermined wavelength are irradiated through an exposure mask having a predetermined pattern shape.
  • the unexposed organic resin layer forming coating film 16 and the high refractive index layer forming coating film 15 are developed with a developing solution to develop an organic resin layer in an unexposed area.
  • the forming coating film 16 and the high refractive index layer forming coating film 15 are simultaneously removed.
  • the developer is not particularly limited as long as it can simultaneously remove the organic resin layer forming coating film 16 and the high refractive index layer forming coating film 15, and an alkaline developer or an acidic developer may be used. it can. Also, the organic resin layer forming coating film 16 and the high refractive index layer forming coating film 15 are not developed simultaneously, but first the organic resin layer forming coating film 16 is developed, and then the high refractive index layer with a different developer. The forming coating film 15 may be developed.
  • the high refractive index layer 5 and the organic resin layer 6 are formed on the first transparent electrode 3 and the second transparent electrode 4 by heating, for example, in an oven at 100 to 300 ° C. (for example, 200 ° C.). To do. Thereby, the laminated body 7 shown in FIG.2 (f) is obtained.
  • substrate 2 for example on a hotplate
  • a coating solution for forming a high refractive index layer (hereinafter also referred to as a coating composition) for forming a high refractive index layer will be described.
  • the coating composition used to form the high refractive index layer is typically obtained by hydrolyzing and condensing a metal alkoxide in an organic solvent in the presence of a metal salt, and further adding a precipitation inhibitor.
  • Composition is typically obtained by hydrolyzing and condensing a metal alkoxide in an organic solvent in the presence of a metal salt, and further adding a precipitation inhibitor.
  • Examples of the metal alkoxide used in the coating composition include silicon (Si), titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), aluminum (Al), magnesium (Mg), and tin (Sn). And alkoxides of metals such as zinc (Zn).
  • silicon alkoxide, partial condensate of silicon alkoxide, and titanium alkoxide is preferable from the viewpoint of easy availability and storage stability of the coating composition.
  • the coating composition is a composition obtained by hydrolyzing and condensing these metal alkoxides in an organic solvent in the presence of a metal salt.
  • the coating composition includes a precipitation inhibitor.
  • the precipitation inhibitor has an effect of preventing the metal salt from being precipitated in the coating film when the coating film is formed.
  • the coating composition contains a titanium alkoxide component
  • the titanium alkoxide when preparing a coating composition containing a titanium alkoxide component, in order to stabilize the titanium alkoxide and improve the storage stability of the coating composition, after mixing and stabilizing the titanium alkoxide and alkylene glycol or monoether thereof, the titanium alkoxide alone Alternatively, it is mixed with silicon alkoxide and hydrolyzed and condensed in the presence of a metal salt.
  • the silicon alkoxide is hydrolyzed in the presence of a metal salt, and then mixed with a titanium alkoxide in which glycols or monoethers thereof are mixed and stabilized in advance. It is preferable to do.
  • the metal alkoxide used in the coating composition is represented by the general formula (I).
  • M 1 (OR 1 ) n (I) (Wherein M 1 represents a metal, R 1 represents a C1-C5 alkyl group, and n represents the valence of M 1 )
  • the silicon alkoxide or the partial condensate thereof at least one selected from one or more compounds represented by the general formula (III) and a partial condensate (pentamer or less) is used.
  • R ′ represents a C1-C5 alkyl group.
  • titanium alkoxide or a partial condensate thereof at least one selected from one or more compounds represented by the general formula (IV) and a partial condensate (pentamer or less) is used.
  • R ′′ represents a C1-C5 alkyl group.
  • Examples of the metal salt used in the coating composition include at least one selected from the compounds represented by the general formula (II).
  • M 2 (X) m (II) (In the formula, M 2 represents a metal, X represents chlorine, nitric acid, sulfuric acid, acetic acid, sulfamic acid, sulfonic acid, acetoacetic acid, acetylacetonate or a basic salt thereof, and m represents the valence of M 2 . ) And metal oxalates used in general formula (II)
  • Examples of the metal M 2 of the metal salt represented by the general formula (II) include aluminum (Al), indium (In), zinc (Zn), zirconium (Zr), bismuth (Bi), lanthanum (La), tantalum ( At least one selected from the group consisting of Ta), yttrium (Y) and cerium (Ce) is preferred.
  • metal nitrates, metal chloride salts and basic salts thereof are particularly preferable.
  • metal nitrates such as aluminum, indium, and cerium are preferred from the viewpoints of availability and storage stability of the coating composition.
  • organic solvent used in the coating composition examples include alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol and t-butanol; esters such as ethyl acetate; ethylene glycol and the like Glycols and ester derivatives thereof; ethers such as diethyl ether; ketones such as acetone, methyl ethyl ketone and cyclohexanone; or aromatic hydrocarbons such as benzene and toluene, etc., which are used alone or in combination .
  • alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol and t-butanol
  • esters such as ethyl acetate
  • ethylene glycol and the like Glycols and ester derivatives thereof examples include ethers such as dieth
  • examples of the alkylene glycol or monoether thereof contained in the organic solvent include ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol and their monomethyl, monoethyl, Examples thereof include monopropyl, monobutyl, and monophenyl ether.
  • the molar ratio of the glycols or monoethers contained in the organic solvent used in the coating composition is less than 1 with respect to the titanium alkoxide, the stability of the titanium alkoxide is less effective, and the storage stability of the coating composition is reduced. Sexuality gets worse.
  • all of the organic solvents used in the coating composition can be the above-described glycols or monoethers thereof.
  • the coating composition does not contain titanium alkoxide, it is not necessary to specifically contain the above-mentioned glycol and / or its monoether.
  • the precipitation inhibitor contained in the coating composition prevents the metal salt from being deposited in the coating film when the coating film is formed.
  • the precipitation inhibitor include at least one selected from the group consisting of N-methyl-pyrrolidone, dimethylformamide, dimethylacetamide, ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, and derivatives thereof. More than seeds can be used.
  • the precipitation inhibitor is used at a ratio of (precipitation inhibitor) / (metal oxide) ⁇ 1 (weight ratio) by converting the metal of the metal salt into a metal oxide.
  • weight ratio is less than 1, the effect of preventing precipitation of the metal salt during formation of the coating film is reduced.
  • the use of a large amount of a precipitation inhibitor has no effect on the coating composition.
  • the precipitation inhibitor may be added when a metal alkoxide, particularly silicon alkoxide, titanium alkoxide, or silicon alkoxide and titanium alkoxide undergoes hydrolysis / condensation reaction in the presence of a metal salt. It may be added after completion of the reaction.
  • a metal alkoxide particularly silicon alkoxide, titanium alkoxide, or silicon alkoxide and titanium alkoxide undergoes hydrolysis / condensation reaction in the presence of a metal salt. It may be added after completion of the reaction.
  • the metal atom (M 1 ) means the sum of plural kinds of metal atoms
  • the metal of the metal salt contained in the coating composition When there are plural kinds of atoms, the metal atom (M 2 ) means the sum of plural kinds of metal atoms.
  • the solid content concentration in the coating composition is preferably in the range of 0.5 to 20 wt% as the solid content when the metal alkoxide and the metal salt are converted as metal oxides.
  • the solid content exceeds 20 wt%, the storage stability of the coating composition is deteriorated and the film thickness control of the metal oxide layer becomes difficult.
  • the solid content is 0.5 wt% or less, the thickness of the obtained metal oxide layer becomes thin, and many coatings are required to obtain a predetermined film thickness.
  • the coating composition is obtained by hydrolyzing and condensing a metal alkoxide represented by M 1 (OR 1 ) n in an organic solvent in the presence of a metal salt (for example, an aluminum salt).
  • a metal salt for example, an aluminum salt.
  • the amount of water used for hydrolysis of silicon alkoxide, titanium alkoxide, or silicon alkoxide and titanium alkoxide is 2 in terms of molar ratio with respect to the total number of moles of silicon alkoxide, titanium alkoxide, or silicon alkoxide and titanium alkoxide. It is preferable to set to 24. More preferably, it is 2-20.
  • the molar ratio (amount of water (mole) / (total number of moles of metal alkoxide)) is 2 or less, the hydrolysis of the metal alkoxide becomes insufficient and the film formability is lowered or the metal obtained This is not preferable because the strength of the oxide film is lowered.
  • the molar ratio is more than 24, polycondensation continues to proceed, which is not preferable because storage stability is lowered. The same applies when other metal alkoxides are used.
  • the above metal alkoxide component may contain the following components as long as the characteristics are not significantly impaired.
  • R 2 j M 3 (OR 3 ) kj (V) (Wherein M 3 is a group consisting of silicon (Si), titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), aluminum (Al), magnesium (Mg) and zinc (Zn).
  • Represents at least one or two or more kinds of metals selected from R 2 may be substituted with a hydrogen atom or a fluorine atom, and may be a halogen atom, vinyl group, glycidoxy group, mercapto group, methacryloxy group, acryloxy
  • a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a group, an isocyanate group, an amino group or a ureido group and which may have a hetero atom
  • R 3 represents a C1 to C5 hydrocarbon group
  • M represents an valence of 3 to 5 of M 3
  • j is 1 or 2 when the valence of k is 3, and any of 1 to 3 when the valence of k is 4 And k If the valence is 5, it is one of 1 to 4.
  • Examples of the metal alkoxide represented by the formula (V) include the following compounds when M 3 is Si.
  • inorganic fine particles silica fine particles, alumina fine particles, titania fine particles, zirconia fine particles, magnesium fluoride fine particles, composite fine particles containing two or more kinds of metals, and the like are preferable, and a colloid solution of these inorganic fine particles is particularly preferable.
  • This colloidal solution may be a dispersion of inorganic fine particle powder in a dispersion medium or a commercially available colloidal solution.
  • the inclusion of inorganic fine particles makes it possible to impart the surface shape of the formed cured film and other functions.
  • the inorganic fine particles preferably have an average particle diameter of 0.001 ⁇ m to 0.2 ⁇ m, and more preferably 0.001 ⁇ m to 0.1 ⁇ m. When the average particle diameter of the inorganic fine particles exceeds 0.2 ⁇ m, the transparency of the cured film formed using the prepared coating liquid may be lowered.
  • the dispersion medium for the inorganic fine particles include water and organic solvents.
  • the pH or pKa is preferably adjusted to 1 to 10, more preferably 2 to 7, from the viewpoint of the stability of the coating solution for film formation.
  • Organic solvents used for the dispersion medium of the colloidal solution include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, 2-methyl-2,4-pentanediol, diethylene glycol, dipropylene glycol, ethylene Alcohols such as glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; ethyl acetate and butyl acetate , Esters such as ⁇ -butyrolactone; and ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or
  • the coexisting metal salt for example, aluminum salt
  • the moisture content is involved in the reaction. Therefore, it is necessary to consider the moisture content of metal salts (for example, aluminum salts).
  • the coating composition is produced by hydrolyzing and condensing a metal alkoxide.
  • the refractive index of the obtained metal oxide layer can be adjusted within a predetermined range. Is possible. For example, when silicon alkoxide and titanium alkoxide are selected as the metal alkoxide, it can be obtained within a predetermined range described later, specifically within a range of 1.45 to 2.1 by adjusting the mixing ratio. It is possible to adjust the refractive index of the resulting metal oxide layer.
  • the composition molar ratio of silicon alkoxide and titanium alkoxide can be determined according to the refractive index. is there.
  • this composition molar ratio is arbitrary, for example, the refractive index of the metal oxide layer from the coating composition obtained by hydrolyzing only silicon alkoxide is a value of about 1.45. And the refractive index of the metal oxide layer from the coating composition obtained by hydrolyzing only a titanium alkoxide is a value of about 2.1.
  • a coating composition is formed using silicon alkoxide and titanium alkoxide at a predetermined ratio according to the refractive index value within the range. Can be manufactured.
  • the refractive index of the obtained metal oxide layer can be adjusted by using other metal alkoxides.
  • the refractive index of the metal oxide layer can be adjusted by selecting film forming conditions in addition to the composition conditions. In this way, it is possible to realize a high hardness of the metal oxide layer and a desired refractive index value.
  • the firing temperature is preferably in the range of 100 ° C. to 300 ° C., more preferably in the range of 150 ° C. to 250 ° C.
  • the refractive index of the metal oxide layer obtained will fluctuate. Specifically, the refractive index of the metal oxide layer can be increased as the amount of ultraviolet irradiation is increased. Therefore, it is possible to select the presence or absence of ultraviolet irradiation in order to achieve a desired refractive index.
  • a desired refractive index can be realized by selecting conditions such as composition, ultraviolet irradiation is not necessary. And when performing ultraviolet irradiation, it is possible to adjust the refractive index of a metal oxide layer by selecting the irradiation amount.
  • a high-pressure mercury lamp when ultraviolet irradiation is necessary to obtain a desired refractive index, for example, a high-pressure mercury lamp can be used. Then, using a high-pressure mercury lamp, total light irradiation 1000 mJ / cm 2 or more dose is preferably at 365nm terms, the dose of 3000mJ / cm 2 ⁇ 10000mJ / cm 2 is more preferable.
  • the UV light source is not particularly specified, and another UV light source can be used. When using another light source, it is only necessary to irradiate the same amount of accumulated light as when using the high-pressure mercury lamp.
  • the coating composition contains a titanium alkoxide component
  • it has a property that the viscosity gradually increases under room temperature storage.
  • careful control over temperature and the like is necessary when precisely controlling the thickness of the metal oxide layer.
  • Such an increase in viscosity becomes more significant as the composition ratio of titanium alkoxide in the coating composition increases. This is presumably because titanium alkoxide has a higher hydrolysis rate than silicon alkoxide and the like, and the condensation reaction is fast.
  • the coating composition contains a titanium alkoxide component
  • the following two production methods are effective for reducing the viscosity change.
  • the production method of 1) is effective because when titanium alkoxide is mixed with glycols, heat is generated, so transesterification occurs between the alkoxide group of titanium alkoxide and the glycols, resulting in hydrolysis / condensation reactions. This is considered to be stabilized.
  • a silicon alkoxide is preliminarily hydrolyzed in the presence of a metal salt, and then mixed with a titanium alkoxide solution mixed with glycols to perform a condensation reaction to obtain a coating composition.
  • a coating composition having a small viscosity change can be obtained.
  • the production method of 2) is effective for the following reasons. That is, the hydrolysis reaction of silicon alkoxide is performed at a high rate, but the subsequent condensation reaction is slower than titanium alkoxide. Therefore, when titanium alkoxide is added quickly after finishing the hydrolysis reaction, the silanol group of the hydrolyzed silicon alkoxide and the titanium alkoxide react uniformly. Thereby, it is thought that the hydrolyzed silicon alkoxide stabilizes the condensation reactivity of titanium alkoxide.
  • a method for mixing silicon alkoxide hydrolyzed in advance and titanium alkoxide has already been attempted.
  • the organic solvent used in the reaction does not contain glycols, a coating composition having excellent storage stability cannot be obtained.
  • the method shown in 2) is also useful when a coating composition is obtained from another metal alkoxide having a high hydrolysis rate and silicon alkoxide.
  • the coating composition described above can be formed into a metal oxide layer by applying a commonly applied coating method to form a coating film.
  • a coating method for example, a dip coating method, a spin coating method, a spray coating method, a brush coating method, a roll transfer method, a screen printing method, an ink jet method, or a flexographic printing method is used.
  • the spin coating method, the slit coating method, the spray coating method, the ink jet method, and the flexographic printing method are particularly preferable from the viewpoint of coating film uniformity.
  • -TEOS Tetraethoxysilane-MPMS: Methacryloxypropyltrimethoxysilane-TTE: Tetraethoxytitanium-AN: Aluminum nitrate nonahydrate-HG: 2-Methyl-2,4-pentanediol (also known as hexylene glycol)
  • -PB Propylene glycol monobutyl ether-PGME: Propylene glycol monomethyl ether-EtOH: Ethanol
  • ⁇ Film Formation Method I> The above-described coating solution for forming a high refractive index layer was subjected to pressure filtration with a membrane filter having a pore diameter of 0.5 ⁇ m, and a film was formed on the substrate by a spin coating method. This substrate was dried on an 80 ° C. hot plate for 100 seconds. Then, temporary baking was performed for 5 minutes on a 150 degreeC hotplate.
  • a negative organic acrylic resin was filtered under pressure through a membrane filter having a pore size of 0.5 ⁇ m, and a film was formed on the substrate by a spin coating method. This substrate was dried for 100 seconds on a hot plate set at 100 ° C.
  • ⁇ Film Formation Method III A negative organic acrylic resin was filtered under pressure with a membrane filter having a pore size of 0.5 ⁇ m, and a film was formed on the substrate by a spin coating method. This substrate was dried for 100 seconds on a hot plate set at 100 ° C.
  • ⁇ Evaluation of refractive index> Using the above-described coating compositions K1 and K2, a silicon substrate (100) is used as a substrate, and a film is formed on this substrate by spin coating so that the film thickness becomes 100 nm after baking, and a hot plate at 80 ° C. Dry for 100 seconds above. Then, after 5 minutes pre-baking on a 150 degreeC hotplate, it baked for 30 minutes in 230 degreeC hot-air circulation type oven, and produced the measurement board
  • a negative organic acrylic resin is used as a substrate, and a silicon substrate (100) is used.
  • a film is formed by spin coating so that the film thickness becomes 100 nm after being baked on a hot plate at 100 ° C. Dry for 100 seconds. Then, it baked for 30 minutes in 230 degreeC hot-air circulation type oven, and produced the measurement board
  • the refractive index at a wavelength of 633 nm was measured using an ellipsometer (DVA-FLVW, manufactured by Mizoji Optical Co., Ltd.).
  • a negative organic acrylic resin was used as a substrate, a silicon substrate (100) was used, and a film was formed on this substrate by a spin coating method, and dried on a hot plate at 100 ° C. for 100 seconds. Then, it baked for 30 minutes in 230 degreeC hot-air circulation type oven, and produced the measurement board
  • a groove was formed by cutting a part of the film surface with a cutter on these substrates, and the film thickness was measured using a fine shape measuring instrument (Surfcoder ET-4000A manufactured by Kosaka Laboratory Ltd.).
  • ⁇ Patterning test> A film was formed on an ITO vapor-deposited glass substrate by the film forming method as shown in the following examples and comparative examples. Next, Cr-deposited glass was placed on the half of the substrate so that a portion exposed to ultraviolet rays and a portion not exposed were formed.
  • irradiation was performed at 4 mW / cm 2 (converted to a wavelength of 365 nm) for 50 seconds using an ultraviolet irradiation device (Mask Aligner PLA-600FA manufactured by Canon Inc.) (total 200 mJ / cm 2 ).
  • the film was immersed in a 1% aqueous potassium hydroxide solution for 1 minute, then washed with water for 10 seconds, excess water droplets were blown off by air blow, and the film surface was visually observed. Evaluation was made with 0 indicating that the film was completely absent in the region, 1 indicating that the film surface was altered, and 2 indicating no change at all.
  • the patterning test was not performed, and baking was performed in an oven at 230 ° C. for 30 minutes.
  • Electrode pattern appearance> The laminates for evaluation and the touch panel for evaluation of the examples and comparative examples in the following table were placed on a black cloth, and were observed visually with the light illuminated from above. As a result of observation, an electrode pattern that cannot be seen was defined as ⁇ Evaluation of electrode pattern appearance ⁇ >. Moreover, although the electrode pattern can be seen, the degree of improvement compared to that having neither the high refractive index layer nor the organic resin layer on the ITO film was defined as ⁇ electrode pattern appearance evaluation ⁇ >. Furthermore, a film equivalent to that having neither a high refractive index layer nor an organic resin layer on the ITO film was evaluated as ⁇ Evaluation of electrode pattern appearance x>.
  • Table 1 shows the evaluation results of Examples and Comparative Examples.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un stratifié comprenant : un substrat transparent (2) ; des électrodes transparentes (3, 4) réalisées sous la forme d'un motif sur le substrat transparent (2) ; une couche à indice de réfraction élevé (5) disposée de façon à recouvrir les électrodes transparentes (3, 4) ; et une couche de résine organique (6) disposée sur la couche à indice de réfraction élevé (5), La couche à indice de réfraction élevé (5) est réalisée sous la forme d'un motif par la forme à formation de motifs de la couche de résine organique (6).
PCT/JP2016/055269 2015-02-24 2016-02-23 Stratifié, panneau tactile et procédé de formation de motifs pour stratifié WO2016136746A1 (fr)

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Cited By (2)

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JPWO2018066214A1 (ja) * 2016-10-06 2019-06-24 アルプスアルパイン株式会社 静電容量式センサ
TWI738849B (zh) * 2016-09-02 2021-09-11 日商東京應化工業股份有限公司 阻劑組成物及阻劑圖型之形成方法

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JP2012081663A (ja) * 2010-10-12 2012-04-26 Sumitomo Metal Mining Co Ltd 透明導電基材及びタッチパネル
WO2012057165A1 (fr) * 2010-10-26 2012-05-03 日産化学工業株式会社 Écran tactile
JP2013057928A (ja) * 2011-09-09 2013-03-28 Tpk Touch Solutions (Xiamen) Inc タッチパネルの積み重ね構造およびタッチパネルの積み重ね構造を基板上に形成する方法

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TWI258349B (en) * 2005-11-16 2006-07-21 Chen Shu Mei Multifunctional shoe cabinet
TWI577523B (zh) * 2011-06-17 2017-04-11 三菱麗陽股份有限公司 表面具有凹凸結構的模具、光學物品、其製造方法、面發光體用透明基材及面發光體
TWM457919U (zh) * 2013-02-08 2013-07-21 Liyitec Inc 觸控面板
WO2016002026A1 (fr) * 2014-07-02 2016-01-07 日立化成株式会社 Film de transfert à réglage d'indice de réfraction photosensible

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Publication number Priority date Publication date Assignee Title
JP2012081663A (ja) * 2010-10-12 2012-04-26 Sumitomo Metal Mining Co Ltd 透明導電基材及びタッチパネル
WO2012057165A1 (fr) * 2010-10-26 2012-05-03 日産化学工業株式会社 Écran tactile
JP2013057928A (ja) * 2011-09-09 2013-03-28 Tpk Touch Solutions (Xiamen) Inc タッチパネルの積み重ね構造およびタッチパネルの積み重ね構造を基板上に形成する方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI738849B (zh) * 2016-09-02 2021-09-11 日商東京應化工業股份有限公司 阻劑組成物及阻劑圖型之形成方法
JPWO2018066214A1 (ja) * 2016-10-06 2019-06-24 アルプスアルパイン株式会社 静電容量式センサ

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