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WO2016159043A1 - Film de transfert, stratifié, dispositif d'entrée de type capacitif et dispositif d'affichage d'image - Google Patents

Film de transfert, stratifié, dispositif d'entrée de type capacitif et dispositif d'affichage d'image Download PDF

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Publication number
WO2016159043A1
WO2016159043A1 PCT/JP2016/060303 JP2016060303W WO2016159043A1 WO 2016159043 A1 WO2016159043 A1 WO 2016159043A1 JP 2016060303 W JP2016060303 W JP 2016060303W WO 2016159043 A1 WO2016159043 A1 WO 2016159043A1
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WIPO (PCT)
Prior art keywords
resin layer
transparent resin
refractive index
high refractive
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2016/060303
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English (en)
Japanese (ja)
Inventor
秀樹 兼岩
壮二 石坂
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Fujifilm Corp
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Fujifilm Corp
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Filing date
Publication date
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Priority to JP2017510075A priority Critical patent/JP6492166B2/ja
Publication of WO2016159043A1 publication Critical patent/WO2016159043A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; 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
    • G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes

Definitions

  • the present invention relates to a transfer film, a laminate, a capacitance type input device, and an image display device.
  • Input devices include a resistance film type and a capacitance type.
  • An electrostatic capacitance type input device has an advantage that a light-transmitting conductive film is simply formed on a single substrate.
  • the capacitance between the electrodes changes.
  • a transparent resin layer is provided by laminating the electrode pattern and the lead wiring for the purpose of protecting the electrode pattern of the capacitive input device and the lead wiring (for example, metal wiring such as copper wire) collected in the frame. It has been.
  • Patent Document 1 includes a temporary support, a transparent resin layer, and a second curable transparent resin layer disposed adjacent to the transparent resin layer in this order, and a second curable transparent resin layer. Has a higher refractive index than the transparent resin layer, and the second curable transparent resin layer has a refractive index of 1.6 or more. According to Patent Document 1, it is described that a transparent laminate having no problem of visually recognizing a transparent electrode pattern can be formed with this configuration.
  • the transparent resin layer is required to be patterned, for example, so as not to cover the terminal portion of the routing wiring in order to connect the terminal portion of the routing wiring of the capacitive input device to other wiring. Yes.
  • a method for forming the pattern of the transparent resin layer it is required to use a photolithography method from the viewpoint of productivity.
  • the problem to be solved by the present invention is that the concealability of a transparent electrode pattern when laminated on a transparent electrode pattern is good, and a laminate having excellent pattern end durability when a pattern is formed after transfer can be formed. It is to provide a transfer film.
  • the problems to be solved by the present invention include a laminate produced using this transfer film, a capacitive input device produced using this transfer film, or comprising this laminate, and this static
  • An object of the present invention is to provide an image display device including a capacitive input device as a constituent element.
  • the present inventors have intensively studied and analyzed.
  • the inventors of the present invention between the undercut entering the pattern ends of the transparent resin layer and the high refractive index transparent resin layer patterned after being laminated on the transparent electrode pattern, and the deterioration of the pattern end durability Correlation was found.
  • the second curable transparent resin layer having the structure described in Patent Document 1 contains a large amount of inorganic particles, it has low adhesion to the substrate and the lead-out wiring, and undercut is likely to occur during pattern development processing.
  • the second curable transparent resin layer was undercut at the pattern edge, it was invaded by harmful substances from the pattern edge, and the internal wiring of the capacitive input device began to deteriorate.
  • the capacitive input device In the field of capacitive input devices, when a person tries to touch the input surface of the capacitive input device with his / her finger, the capacitive input device is often gripped, and harmful substances such as sweat Is often attached to the pattern edge existing in the frame portion of the capacitance-type input device. Therefore, the pattern edge durability of the transparent resin layer and the high refractive index transparent resin layer is a practically important performance.
  • the present inventors have found that the swelling and shrinkage of the transparent resin layer and the high refractive index transparent resin layer greatly affect the occurrence of undercuts at the pattern edges of the transparent resin layer and the high refractive index transparent resin layer. It has been found that the occurrence of undercut at the pattern edge can be suppressed by reducing the swelling and shrinkage of the transparent resin layer and the high refractive index transparent resin layer. That is, the concealability of the transparent electrode pattern when the transfer film is laminated on the transparent electrode pattern is good by setting the swelling ratio of the two layers comprising the transparent resin layer and the high refractive index transparent resin layer within a specific range. And it came to discover that the transfer film excellent in pattern edge durability at the time of forming a pattern after transfer can be provided.
  • the present invention which is a specific means for solving the above problems, is as follows.
  • a temporary support A transparent resin layer; It has a high refractive index transparent resin layer arranged adjacent to be in direct contact with the transparent resin layer in this order, The refractive index of the high refractive index transparent resin layer is higher than the refractive index of the transparent resin layer, A transfer film in which the swelling ratio of the two layers comprising the transparent resin layer and the high refractive index transparent resin layer is 6.0% or less; However, the swelling rate of the two layers comprising the transparent resin layer and the high refractive index transparent resin layer is determined by transferring the high refractive index transparent resin layer and the transparent resin layer from the transfer film onto the copper foil of the PET film on which the copper foil is laminated.
  • the transparent resin layer preferably has 2.50 ⁇ 10 ⁇ 3 pieces / g or more of a crosslinkable group.
  • the transparent resin layer preferably contains a photopolymerization initiator having a solid content ratio of 0.3% by mass or more.
  • the transfer film according to any one of [1] to [3] preferably has an I / O value, which is a measure of hydrophilicity / hydrophobicity of the transparent resin layer, of 1.10 or less.
  • the transfer film according to any one of [1] to [4] preferably has a C / H ratio of 0.68 or more, which is a ratio of carbon to hydrogen in the mass of the transparent resin layer. .
  • the acid value of the transparent resin layer is preferably 35 to 80 mgKOH / g.
  • the transparent resin layer preferably contains a binder polymer having an acid value of 55 to 150 mgKOH / g.
  • the transparent resin layer preferably has a thickness of 4 to 15 ⁇ m.
  • the high refractive index transparent resin layer preferably contains a metal oxidation inhibitor.
  • the metal oxidation inhibitor preferably has an imidazole ring, a triazole ring, or a condensed ring of these with another aromatic ring in the molecule.
  • the high refractive index transparent resin layer preferably has a refractive index of 1.60 or more.
  • the high refractive index transparent resin layer preferably contains metal oxide particles having a solid content ratio of 40% by mass or more.
  • the thickness of the high refractive index transparent resin layer is preferably 0.20 ⁇ m or less.
  • the swelling ratio of the two layers including the transparent resin layer and the high refractive index transparent resin layer is 1.5% or more. .
  • the transfer film according to any one of [1] to [14] is preferably a dry resist film.
  • the laminate according to [16] preferably has a C / H ratio of 0.68 or more, which is a ratio of carbon and hydrogen in the mass of the transparent resin layer.
  • the high refractive index transparent resin layer preferably contains a metal oxidation inhibitor.
  • the metal oxidation inhibitor preferably has an imidazole ring, a triazole ring, or a condensed ring of these and another aromatic ring in the molecule.
  • the high refractive index transparent resin layer preferably contains metal oxide particles having a solid content ratio of 40% by mass or more.
  • the laminate according to any one of [16] to [20] includes a high refractive index transparent resin for a transfer film according to any one of [1] to [15] on an electrode pattern. It is preferable to have a layer and a transparent resin layer in this order.
  • the electrode pattern is preferably an electrode pattern positioned on a transparent film substrate.
  • the laminate according to [22] preferably has an electrode pattern, a high refractive index transparent resin layer, and a transparent resin layer on both surfaces of the transparent film substrate, respectively.
  • An image display device comprising the capacitive input device according to [24] or [25] as a constituent element.
  • a transfer film capable of forming a laminate that has good concealability of a transparent electrode pattern when laminated on a transparent electrode pattern and excellent pattern end durability when a pattern is formed after transfer. can do.
  • FIG. 1 It is a section schematic diagram showing an example of composition of a transfer film of the present invention. It is a top view which shows another example of a structure of the electrostatic capacitance type input device of this invention, and shows the aspect containing the terminal part (terminal part) of the routing wiring which is pattern-exposed and is not covered with the transparent resin layer.
  • FIG.17 (A) represents the aspect of undercut depth U> 0
  • FIG. 17C shows a mode in which the undercut depth U ⁇ 0.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the transfer film of the present invention has a temporary support, a transparent resin layer, and a high refractive index transparent resin layer disposed adjacently so as to be in direct contact with the transparent resin layer.
  • the refractive index of the layer is higher than the refractive index of the transparent resin layer, and the swelling ratio of the two layers comprising the transparent resin layer and the high refractive index transparent resin layer is 6.0% or less.
  • the swelling rate of the two layers comprising the transparent resin layer and the high refractive index transparent resin layer is determined by transferring the high refractive index transparent resin layer and the transparent resin layer from the transfer film onto the copper foil of the PET film on which the copper foil is laminated.
  • the transfer film of the present invention forms a laminate that has excellent concealability of the transparent electrode pattern when laminated on the transparent electrode pattern, and excellent pattern end durability when the pattern is formed after transfer. it can.
  • the configuration of the present invention does not cause much shrinkage at the pattern ends of the transparent resin layer and the high refractive index transparent resin layer after irradiation with light (ultraviolet rays) and heating, and is harmful to salt water and the like.
  • the term “transparent” means that the average transmittance of visible light having a wavelength of 400 nm to 700 nm is 80% or more. Therefore, the transparent layer refers to a layer having an average transmittance of visible light having a wavelength of 400 nm to 700 nm of 80% or more. The average transmittance of visible light having a wavelength of 400 nm to 700 nm of the transparent layer is preferably 90% or more. The average transmittance of visible light having a wavelength of 400 nm to 700 nm of the transfer film of the present invention or the transparent layer of the transfer film is measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
  • the durability of the central portion of the transparent resin layer and the high refractive index transparent resin layer can also be improved, and more preferably, the wet heat durability after the salt water is applied to the central portion can be improved.
  • the wet heat durability after the application of salt water in the center is an important performance in practical use. Sweat that adheres when a human touches the input surface of the capacitive input device with a finger may penetrate into the capacitive input device. If the capacitive input device is subsequently used or charged in a humid and hot environment, the inside of the capacitive input device becomes a high temperature and high humidity environment. Therefore, the transparent resin layer and the high refractive index transparent resin It is preferable that the wet heat durability after the salt water provision of the center part of a layer is high.
  • the transfer film of the present invention is preferably for a transparent insulating layer or a transparent protective layer of a capacitive input device.
  • the transparent resin layer is preferably in an uncured state.
  • a laminated pattern of a protective film for an electrode of a capacitive input device is formed on the transparent electrode pattern by a photolithography method.
  • a transfer film for forming a laminated pattern of a refractive index adjusting layer and an overcoat layer transparent protective layer.
  • the swelling ratio of the two layers comprising the transparent resin layer and the high refractive index transparent resin layer is 6.0% or less, and preferably 4.5% or less from the viewpoint of pattern end durability.
  • the swelling ratio of the two layers comprising the transparent resin layer and the high refractive index transparent resin layer is preferably 1.5% or more from the viewpoint of developability.
  • the swelling ratio of the two layers consisting of the transparent resin layer and the high refractive index transparent resin layer is as follows. The value which expressed the ratio with respect to the film thickness before immersion of the variation
  • the “swelling ratio” referred to in the present invention is a value expressed as a percentage of the film thickness before immersion of the amount of change in film thickness before and after the target layer is immersed in a specific liquid.
  • the swelling rate is positive when the layer swells and takes a negative value when the layer shrinks.
  • the film thickness of the layer can be measured with, for example, a stylus film thickness meter.
  • Temporal support> There is no restriction
  • the thickness of the temporary support is not particularly limited, and is generally in the range of 5 to 200 ⁇ m. In view of ease of handling and versatility, the thickness of 10 to 150 ⁇ m is particularly preferable.
  • the temporary support is preferably a film, and more preferably a resin film.
  • a flexible material that does not cause significant deformation, shrinkage, or elongation under pressure or under pressure and heat can be used.
  • the temporary support satisfying this property include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film, and among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.
  • the temporary support may be transparent or may contain dyed silicon, alumina sol, chromium salt, zirconium salt or the like. Further, the temporary support can be imparted with conductivity by the method described in JP-A-2005-221726.
  • the transparent resin layer is arranged adjacent to be in direct contact with the high refractive index transparent resin layer.
  • the transparent resin layer may be disposed adjacent to the temporary support so as to be in direct contact with each other, or may be laminated via the temporary support with another layer, but is adjacent to the temporary support so as to be in direct contact with the temporary support.
  • the transparent resin layer may be thermosetting, photocurable, thermosetting and photocurable.
  • the transparent resin layer and the high refractive index transparent resin layer described later are a thermosetting transparent resin layer and a photocurable transparent resin layer, and are easily photocured after transfer and can be formed into a film. It is preferable from the viewpoint of thermosetting and imparting wet heat durability after application of salt water.
  • the acid value of the transparent resin layer is preferably 35 to 80 mgKOH / g, more preferably 35 to 70 mgKOH / g, and particularly preferably 40 to 60 mgKOH / g.
  • the acid value of the transparent resin layer is preferably 35 mgKOH / g or more from the viewpoint that the undercut depth does not become too small and developability can be improved.
  • the “acid value” as used in the present invention refers to the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids, etc. contained in 1 g of the target sample.
  • the acid value of the transparent resin layer can be determined according to a method shown in JIS (Japan Industrial Standards) K 0070: 1992.
  • the thickness of the transparent resin layer can be set to 1 to 20 ⁇ m, for example.
  • the thickness of the transparent resin layer is preferably 4 to 15 ⁇ m, and more preferably 5 to 12 ⁇ m.
  • the wet heat durability of the transparent resin layer after transfer (especially after exposure, development, and heating) after applying salt water can be improved, and the durability of the center is improved. can do.
  • the developability can be improved when the thickness of the transparent resin layer is 15 ⁇ m or less.
  • the above-mentioned transparent resin layer is preferably used in the image display portion of the capacitance-type input device.
  • the thickness of the transparent resin layer is determined by the method described in Examples below using a reflection spectral film thickness meter.
  • the transparent resin layer preferably has 2.50 ⁇ 10 ⁇ 3 pieces / g or more of a crosslinkable group from the viewpoint of reducing the swelling ratio and improving the durability of the pattern edge. It is more preferable to have a crosslinkable group of ⁇ 10 ⁇ 3 / g or more and 1.00 ⁇ 10 ⁇ 2 / g or less.
  • the amount of the crosslinkable group can be calculated by dissolving the transparent resin layer sample in a suitable solvent and quantifying the various crosslinkable groups by analysis such as NMR (Nuclear Magnetic Resonance) or FT-IR (Fourier Transform Infrared Spectrometer). Moreover, you may obtain
  • the transfer film of the present invention has an I / O value of 1.10 or less, which is a measure of the hydrophilicity / hydrophobicity of the transparent resin layer, from the viewpoint that the swelling rate can be reduced, the pattern end durability can be improved, and the central portion durability can also be improved. It is preferable that it is 0.80 to 0.99.
  • the “I / O value” referred to in the present invention means the degree of hydrophilicity / hydrophobicity exhibited by a compound by integrating the organic degree and inorganic degree determined for each functional group according to the number of functional groups and taking the ratio. It is a parameter that serves as an index representing the scale.
  • I represents inorganicity
  • O represents organicity
  • I / O values are described in detail in “Organic Conceptual Diagram” (Yoshio Koda, Sankyo Publishing, 1984). The I / O value can be adjusted by changing the type of the photopolymerizable compound or binder polymer.
  • the C / H ratio which is the ratio of carbon to hydrogen in the mass of the transparent resin layer
  • the C / H ratio can be reduced from the viewpoint that the swelling ratio can be reduced, the pattern end durability can be improved, and the central portion durability can also be improved. .68 or more is preferable, and 0.69 to 0.75 is more preferable.
  • the “C / H ratio” in the present invention refers to the ratio of the mass of carbon atoms and hydrogen atoms to the total mass of the target layer.
  • Various elemental analysis methods are used as a method for measuring the ratio of carbon atoms and hydrogen atoms. As a typical means, for example, a method of burning a predetermined amount of sample and measuring the weight of generated water and carbon dioxide can be mentioned. The higher the C / H ratio, the lower the I / O value.
  • the refractive index of the high refractive index transparent resin layer is higher than the refractive index of the transparent resin layer.
  • the refractive index of the transparent resin layer is preferably 1.50 to 1.53, more preferably 1.50 to 1.52, and particularly preferably 1.51 to 1.52. .
  • the refractive index is measured by comparing the spectral reflectance spectrum calculated assuming the thickness and refractive index of the target layer with the measured spectral reflectance spectrum, and minimizing the difference between the two by the curve fitting method. Find the thickness and refractive index.
  • a spectroscopic reflection film thickness meter FE-3000 manufactured by Otsuka Electronics Co., Ltd. is used as an apparatus capable of performing both the measurement and the calculation.
  • the transfer film of the present invention may be a negative type material or a positive type material.
  • the transfer film of the present invention is preferably a negative material.
  • the method for controlling the refractive index of the transparent resin layer is not particularly limited, but a transparent resin layer having a desired refractive index is used alone, or a transparent resin layer to which particles such as metal particles and metal oxide particles are added is used. Alternatively, a composite of a metal salt and a polymer can be used.
  • an additive may be used for the transparent resin layer.
  • the additive include surfactants described in paragraph 0017 of Japanese Patent No. 4502784, paragraphs 0060 to 0071 of JP-A-2009-237362, and thermal polymerization described in paragraph 0018 of Japanese Patent No. 4502784. Further, other additives described in paragraphs 0058 to 0071 of JP-A No. 2000-310706 can be mentioned.
  • the transfer film of the present invention is a negative type material
  • the transfer film of the present invention may be a positive type material.
  • the transfer film of the present invention preferably contains a binder polymer in the transparent resin layer.
  • a binder polymer used for a transparent resin layer It is preferable that it is resin which has an acid group.
  • the resin having an acid group that can be used is not particularly limited as long as it does not contradict the gist of the present invention, and can be appropriately selected from known ones.
  • the resin having an acid group also includes a resin in a salt state in which the acid group is neutralized.
  • the resin having an acid group is preferably a resin having a monovalent acid group (such as a carboxyl group).
  • the resin having an acid group is preferably an alkali-soluble resin.
  • the alkali-soluble resin is a linear organic polymer, and is a group that promotes at least one alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having an acid group (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. As the acid group, a carboxyl group is preferable.
  • the binder polymer used for the transparent resin layer is preferably an acrylic resin, and more preferably a carboxyl group-containing acrylic resin.
  • any polymer component can be used without particular limitation, but from the viewpoint of use as a protective film for a transparent electrode of a capacitive input device, surface hardness, heat resistance Highly preferred are alkali-soluble resins, and among the alkali-soluble resins, there can be mentioned known photosensitive siloxane resin materials.
  • the binder polymer contained in the transparent resin layer is preferably an acrylic resin.
  • Both the binder polymer contained in the transparent resin layer and the resin or binder polymer having an acid group contained in the high refractive index transparent resin layer described later contain an acrylic resin, so that the transparent resin layer and the high refractive index transparent resin layer It is preferable from the viewpoint of improving interlayer adhesion before and after transfer.
  • the preferable range of the above-mentioned binder polymer of the transparent resin layer will be specifically described.
  • the binder polymer (also referred to as “binder” or “polymer”) used in the transparent resin layer is not particularly limited as long as it does not contradict the gist of the present invention, and can be appropriately selected from known ones. Polymers described in paragraph 0025 of 2011-95716 and polymers described in paragraphs 0033 to 0052 of JP 2010-237589 can be used.
  • the transparent resin layer preferably contains a binder polymer having an acid value of 55 to 150 mgKOH / g, the acid value of the binder polymer is more preferably 60 to 150 mgKOH / g, and 70 to 120 mgKOH / g. Particularly preferred is g.
  • the “acid value” as used in the present invention refers to the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids, etc. contained in 1 g of the target sample.
  • Examples of the method for measuring the acid value of the binder polymer include the same method as the method for measuring the acid value of the transparent resin layer.
  • the acid value of the binder polymer may be a theoretical acid value calculated by a calculation method described in the following literature or the like. . JP 2004-149806 A [0063], JP 2012-211228 A [0070].
  • the transparent resin layer may contain a polymer latex as a binder polymer.
  • the polymer latex referred to here is one in which water-insoluble polymer particles are dispersed in water.
  • the polymer latex is described, for example, in Soichi Muroi “Chemistry of Polymer Latex (published by Kobunshi Shuppankai (Showa 48))”.
  • Polymer particles that can be used include acrylic, vinyl acetate, rubber (for example, styrene-butadiene, chloroprene), olefin, polyester, polyurethane, polystyrene, and copolymers thereof. Particles are preferred. It is preferable to increase the bonding force between the polymer chains constituting the polymer particles.
  • As means for strengthening the bonding force between polymer chains there are a method using an interaction caused by hydrogen bonding and a method of generating a covalent bond.
  • a monomer having a polar group in the polymer chain by copolymerization or graft polymerization.
  • the polar groups of the binder polymer include carboxyl groups (contained in acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, partially esterified maleic acid, etc.), primary, secondary and tertiary amino groups , Ammonium base, sulfonic acid group (styrene sulfonic acid group and the like), and the like.
  • the binder polymer which is a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more has at least a carboxyl group.
  • a preferable range of the copolymerization ratio of these polar group-containing monomers is 5 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 20 to 35% by mass with respect to 100% by mass of the polymer. is there.
  • the preferable copolymerization ratio of the monomer having a carboxyl group is 5 to 50% by mass, more preferably 5 to 50% by mass with respect to 100% by mass of the polymer.
  • an epoxy compound As means for generating a covalent bond, an epoxy compound, a blocked isocyanate, an isocyanate, at least one of a hydroxyl group, a carboxyl group, a primary or secondary amino group, an acetoacetyl group and a sulfonic acid group, Examples include a method of reacting at least one of a vinyl sulfone compound, an aldehyde compound, a methylol compound, a carboxylic acid anhydride, and the like.
  • the weight average molecular weight of the polymer is preferably 10,000 or more, more preferably 20,000 to 100,000.
  • the polymer latex that can be used in the present invention may be obtained by emulsion polymerization or may be obtained by emulsification.
  • the method for preparing these polymer latexes is described, for example, in “Emulsion Latex Handbook” (edited by Emulsion Latex Handbook Editorial Committee, published by Taiseisha Co., Ltd. (Showa 50)).
  • Examples of the polymer latex that can be used in the present invention include an alkyl acrylate copolymer ammonium (trade name: Jurimer AT-210, manufactured by Toagosei Co., Ltd.), and an alkyl acrylate copolymer ammonium (trade name: Jurimer ET-410, Toagosei Co., Ltd.).
  • alkyl acrylate copolymer ammonium (trade name: Jurimer AT-510, manufactured by Toagosei Co., Ltd.) and polyacrylic acid (product name: Jurimer AC-10L, manufactured by Toagosei Co., Ltd.) are neutralized with ammonia. And an emulsified product.
  • the transparent resin layer preferably contains a photopolymerizable compound having an ethylenically unsaturated group.
  • the photopolymerizable compound having an ethylenically unsaturated group only needs to have at least one ethylenically unsaturated group as a photopolymerizable group, and has an epoxy group in addition to the ethylenically unsaturated group. Also good.
  • the photopolymerizable compound of the transparent resin layer includes a compound having a (meth) acryloyl group.
  • the photopolymerizable compound used for the transfer film may be used alone or in combination of two or more, but it is possible to use a combination of two or more transparent resin layers after transfer. From the viewpoint of improving the wet heat durability after the application of salt water after exposure.
  • the photopolymerizable compound used for the transfer film of the present invention is a combination of a tri- or higher functional photopolymerizable compound and a bifunctional photopolymerizable compound. Brine after exposure of the transparent resin layer after transfer From the viewpoint of improving wet heat durability after application, it is preferable.
  • the bifunctional photopolymerizable compound is preferably used in the range of 10 to 90% by mass, more preferably in the range of 20 to 85% by mass with respect to all the photopolymerizable compounds, and 30 to 80% by mass. It is particularly preferable to use in the range of%.
  • the trifunctional or higher functional photopolymerizable compound is preferably used in the range of 10 to 90% by mass, more preferably in the range of 15 to 80% by mass, with respect to all the photopolymerizable compounds. It is particularly preferable to use in the range of mass%.
  • the transfer film preferably contains at least a compound having two ethylenically unsaturated groups and a compound having at least three ethylenically unsaturated groups as the photopolymerizable compound, and has two (meth) acryloyl groups. More preferably, it comprises at least a compound and a compound having at least three (meth) acryloyl groups.
  • the transfer film of the present invention is such that at least one of the photopolymerizable compounds having an ethylenically unsaturated group contains a carboxyl group, the photopolymerizability having a carboxyl group of the binder polymer and an ethylenically unsaturated group.
  • a commercially available compound can be used.
  • Aronix TO-2349 manufactured by Toagosei Co., Ltd.
  • Aronix M-520 manufactured by Toagosei Co., Ltd.
  • Aronix M-510 manufactured by Toagosei Co., Ltd.
  • the like can be preferably used.
  • the photopolymerizable compound having an ethylenically unsaturated group containing a carboxyl group is preferably used in the range of 1 to 50% by mass with respect to all the photopolymerizable compounds, and used in the range of 1 to 30% by mass. It is more preferable to use in the range of 5 to 15% by mass. It is preferable that a urethane (meth) acrylate compound is included as the above-mentioned photopolymerizable compound.
  • the mixing amount of the urethane (meth) acrylate compound is preferably 10% by mass or more, and more preferably 20% by mass or more with respect to all the photopolymerizable compounds.
  • the number of functional groups of the photopolymerizable group is preferably 3 or more, and more preferably 4 or more.
  • the photopolymerizable compound having a bifunctional ethylenically unsaturated group is not particularly limited as long as it is a compound having two ethylenically unsaturated groups in the molecule, and a commercially available (meth) acrylate compound can be used.
  • tricyclodecane dimethanol diacrylate A-DCP Shin-Nakamura Chemical Co., Ltd.
  • tricyclodecane dimenanol dimethacrylate DCP Shin-Nakamura Chemical Co., Ltd.
  • 1,9-nonanediol di Acrylate A-NOD-N, Shin-Nakamura Chemical Co., Ltd.
  • 1,6-hexanediol diacrylate A-HD-N, Shin-Nakamura Chemical Co., Ltd.
  • the photopolymerizable compound having a trifunctional or higher functional ethylenically unsaturated group is not particularly limited as long as it is a compound having three or more ethylenically unsaturated groups in the molecule.
  • dipentaerythritol (tri / tetra / penta / (Hexa) acrylate, pentaerythritol (tri / tetra) acrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, isocyanuric acid acrylate and other (meth) acrylate compounds can be used, but span between (meth) acrylates Longer lengths are preferred.
  • skeletons such as the aforementioned dipentaerythritol (tri / tetra / penta / hexa) acrylate, pentaerythritol (tri / tetra) acrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, isocyanuric acid acrylate ( Caprolactone-modified compounds of meth) acrylate compounds (KAYARAD DPCA manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified compounds (KAYARAD RP-produced by Nippon Kayaku Co., Ltd.) 1040, Shin-Nakamura Chemical Co., Ltd.
  • Tri- or more functional urethane (meth) acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.) And the like can be preferably used.
  • the photopolymerizable compound used for the transfer film preferably has a molecular weight of 200 to 3000, more preferably 250 to 2600, and particularly preferably 280 to 2200.
  • the pattern of the transparent resin layer can be easily formed.
  • the photopolymerization initiator used for the transparent resin layer the photopolymerization initiators described in paragraphs 0031 to 0042 described in JP 2011-95716 A can be used.
  • the transparent resin layer preferably contains a photopolymerization initiator having a solid content ratio of 0.3% by mass or more from the viewpoint of suppressing the expansion rate and improving the pattern end durability. It is more preferable that the transparent resin layer contains a photopolymerization initiator of 0.6% by mass or more in terms of the solid content ratio, and particularly preferably 0.7% by mass or more.
  • the transparent resin layer preferably contains a photopolymerization initiator of 10% by mass or less in terms of the solid content ratio, and more preferably 5% by mass or less from the viewpoint of improving the patterning property of the laminate of the present invention.
  • the transparent resin layer preferably has a blocked isocyanate.
  • the blocked isocyanate means “a compound having a structure in which an isocyanate group of an isocyanate is protected (masked) with a blocking agent”.
  • the dissociation temperature of the blocked isocyanate is preferably 100 ° C. to 160 ° C., and particularly preferably 130 to 150 ° C.
  • the dissociation temperature of the blocked isocyanate in the present specification refers to “according to the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.). "Endothermic peak temperature”.
  • Examples of the blocking agent having a dissociation temperature of 100 ° C. to 160 ° C. or less include pyrazole compounds (3,5-dimethylpyrazole, 3-methylpyrazole, 4-bromo-3,5-dimethylpyrazole, 4-nitro-3,5-dimethyl Pyrazole, etc.), active methylene compounds (malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)), triazole compounds (1,2,4-triazole, etc.) ), Oxime compounds (formald oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime) and the like.
  • oxime compounds and pyrazole compounds are preferable, and oxime compounds are particularly preferable.
  • the blocked isocyanate has an isocyanurate structure from the viewpoint of the brittleness of the film and the adhesion of the substrate.
  • the oxime compound A is preferable from the viewpoint of easily making the dissociation temperature within a preferable range and improving the developability compared to the compound B having no oxime structure.
  • the number of blocked isocyanate groups in the blocked isocyanate is preferably 1 to 10, more preferably 2 to 6, and particularly preferably 3 to 4.
  • blocked isocyanate used in the transfer film of the present invention include the following compounds.
  • the blocked isocyanate used in the present invention is not limited to the following specific examples.
  • blocked isocyanate used in the transfer film of the present invention a commercially available blocked isocyanate can be exemplified.
  • Takenate (registered trademark) B870N (made by Mitsui Chemicals), which is a methyl ethyl ketone oxime blocked form of isophorone diisocyanate
  • Duranate (registered trademark) MF-K60B, TPA-B80E (Asahi Kasei Chemicals) which is a hexamethylene diisocyanate-based blocked isocyanate compound For example).
  • the blocked isocyanate used for the transfer film preferably has a molecular weight of 200 to 3000, more preferably 250 to 2600, and particularly preferably 280 to 2200.
  • the transparent resin layer preferably contains 0.01 to 0.5% by mass of a fluorine-containing surfactant based on the solid content of the transparent resin layer.
  • a fluorine-containing surfactant based on the solid content of the transparent resin layer.
  • the transparent resin layer contains a surfactant containing fluorine atoms
  • a surfactant containing fluorine atoms when the transparent resin layer is applied and dried, a thin layer of surfactant containing fluorine atoms is formed on the surface of the transparent resin layer, It was newly found that when this becomes a protective layer and a high refractive index transparent resin layer is applied, interlayer mixing with the transparent resin layer can be suppressed.
  • a surfactant containing 0.01% by mass or more of fluorine atoms with respect to the solid content of the transparent resin layer this effect is remarkably obtained. By including the agent, this effect can be obtained more remarkably.
  • the transparent resin layer preferably contains 0.01 to 0.5% by mass, more preferably 0.02 to 0.4% by mass, of a surfactant containing fluorine atoms, based on the solid content of the transparent resin layer. Particularly preferred. In order to maintain good adhesion between the high refractive index transparent resin layer and the transparent electrode pattern, it is preferable to contain a surfactant containing fluorine atoms in an amount of 0.5% by mass or less based on the solid content of the transparent resin layer. More preferably, the content is 0.4% by mass or less. Furthermore, when an acrylic resin is selected as the resin of the transparent resin layer and a surfactant containing a fluorine atom is used in combination, this effect can be obtained more remarkably.
  • surfactants containing fluorine atoms that are preferably used in the transparent resin layer include surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362. it can.
  • a surfactant containing a fluorine atom preferably used for the transparent resin layer a commercially available surfactant containing a fluorine atom can be used. In particular, the following surfactants containing fluorine atoms are preferred.
  • the aforementioned transparent resin layer may or may not contain particles (preferably metal oxide particles) for the purpose of adjusting the refractive index and light transmittance.
  • metal oxide particles can be included in an arbitrary ratio depending on the type of polymer or photopolymerizable compound used.
  • the metal oxide particles are preferably contained in an amount of 0 to 35% by mass, more preferably 0 to 10% by mass, based on the transparent resin layer. It is particularly preferred. Since the metal oxide particles have high transparency and light transmittance, a transparent resin layer having a high refractive index and excellent transparency can be obtained.
  • the refractive index of the metal oxide particles is preferably higher than the refractive index of the transparent resin layer not including the metal oxide particles. That is, the above-described metal oxide particles preferably have a refractive index higher than that of a composition made of a material obtained by removing the particles from the transparent resin layer.
  • the metal of the metal oxide particles described above includes metalloids such as B, Si, Ge, As, Sb, and Te.
  • the light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb.
  • Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable.
  • Titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / Tin oxide and antimony / tin oxide are more preferable, titanium oxide, titanium composite oxide, and zirconium oxide are more preferable, and titanium oxide and zirconium oxide are particularly preferable.
  • Titanium oxide is particularly preferably a rutile type having a high refractive index. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.
  • the metal oxide particles described above may be used alone or in combination of two or more.
  • the transparent resin layer preferably does not contain metal oxide particles, but the case where metal oxide particles are included is also included in the present invention.
  • Examples of the metal oxide particles when the transparent resin layer includes metal oxide particles include ZrO 2 particles, Nb 2 O 5 particles, and TiO 2 particles.
  • the transfer film of the present invention has a high refractive index transparent resin layer disposed adjacent to the transparent resin layer.
  • the high refractive index transparent resin layer may be thermosetting, photocurable, thermosetting and photocurable.
  • the high refractive index transparent resin layer is preferably at least a thermosetting transparent resin layer, from the viewpoint that it can be thermoset after transfer to impart wet heat durability of the film, and the thermosetting transparent resin layer and photocurable
  • the transparent resin layer is more preferable from the viewpoint that it can be easily photocured after transfer to form a film and can be thermoset after film formation to impart wet heat durability of the film.
  • the transfer film of the present invention has a high refractive index transparent resin layer disposed adjacently so as to be in direct contact with the transparent resin layer, and the refractive index of the high refractive index transparent resin layer is higher than the refractive index of the transparent resin layer described above. Is also expensive.
  • the fact that the refractive index of the high refractive index transparent resin layer is higher than the refractive index of the transparent resin layer can also be confirmed by actually measuring the refractive index of each layer. It can also be confirmed based on the fact that a high refractive index substance such as fine particles is contained.
  • the difference in refractive index between the transparent electrode pattern (preferably Indium Tin Oxide; ITO) and the above-described high refractive index transparent resin layer and the difference in refractive index between the above high refractive index transparent resin layer and the above transparent resin layer are small.
  • the difference between the refractive index of the high refractive index transparent resin layer and the refractive index of the transparent resin layer is preferably 0.03 to 0.30, and more preferably 0.05 to 0.20.
  • the transparent resin layer is curable, even if the high refractive index transparent resin layer is laminated without curing the transparent resin layer after laminating the transparent resin layer, the layer fraction becomes good and the above The transparent electrode pattern concealing property can be improved by this mechanism. Furthermore, in this case, after transferring the refractive index adjusting layer (that is, the transparent resin layer and the high refractive index transparent resin layer) from the transfer film onto the transparent electrode pattern, the refractive index adjusting layer (preferably a transparent resin layer, more preferably transparent). The resin layer and the high refractive index transparent resin layer) can be developed into a desired pattern by photolithography.
  • the refractive index adjusting layer that is, the transparent resin layer and the high refractive index transparent resin layer
  • Photolithography is preferably performed at least on the transparent resin layer that is closer to the outside than the high refractive index transparent resin layer after transfer.
  • the high refractive index transparent resin layer that becomes a layer closer to the inside than the transparent resin layer after the transfer may not have photolithographic properties.
  • a transparent resin layer has sclerosis
  • the refractive index of the high refractive index transparent resin layer of the transfer film of the present invention needs to be adjusted by the refractive index of the transparent electrode pattern.
  • the refractive index of the transparent electrode pattern is in the range of 1.8 to 2.0, for example, when formed using an oxide of In and Sn (ITO)
  • the ITO second transparent resin layer 20 The refractive index is preferably 1.60 or more.
  • the upper limit of the refractive index is not particularly limited, but is preferably 2.1 or less, more preferably 1.78 or less, and even more preferably 1.74 or less.
  • the refractive index of the transparent electrode pattern exceeds 2.0, for example, when formed using an oxide of In and Zn (IZO), the refractive index of the second transparent resin layer 20 is 1.7. It is preferably at least 1.85.
  • the thickness of the high refractive index transparent resin layer is preferably 0.20 ⁇ m or less (200 nm or less) from the viewpoint of improving the transparency of the transparent electrode pattern, and more preferably 110 nm or less.
  • the film thickness of the high refractive index transparent resin layer is preferably 20 nm or more.
  • the film thickness of the aforementioned high refractive index transparent resin layer is particularly preferably from 55 to 100 nm, more preferably from 60 to 100 nm, even more preferably from 70 to 100 nm.
  • the thickness of the high refractive index transparent resin layer is determined by the method described in Examples below using a reflection spectral film thickness meter.
  • the high refractive index transparent resin layer preferably contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator.
  • the high refractive index transparent resin layer of the transfer film of the present invention may be a negative type material or a positive type material.
  • the high refractive index transparent resin layer includes metal oxide particles, a binder polymer (preferably an alkali-soluble resin), a photopolymerizable compound, light It preferably contains a polymerization initiator. Furthermore, an additive etc. are used and it is not restricted to this.
  • the method for controlling the refractive index of the high refractive index transparent resin layer is not particularly limited, but a high refractive index transparent resin layer having a desired refractive index is used alone, or particles such as metal particles and metal oxide particles are added. It is possible to use a transparent resin layer having a high refractive index, or a composite of a metal salt and a polymer.
  • an additive may be used for the above-described high refractive index transparent resin layer.
  • the additive include surfactants described in paragraph 0017 of Japanese Patent No. 4502784, paragraphs 0060 to 0071 of JP-A-2009-237362, and thermal polymerization described in paragraph 0018 of Japanese Patent No. 4502784. Further, other additives described in paragraphs 0058 to 0071 of JP-A No. 2000-310706 can be mentioned.
  • the transfer film of the present invention is a negative type material
  • the transfer film of the present invention may be a positive type material.
  • the transfer film of the present invention is a positive type material, for example, materials described in JP-A-2005-221726 are used for the high refractive index transparent resin layer, and the present invention is not limited thereto.
  • the high refractive index transparent resin layer preferably contains an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group.
  • the ammonium salt of the monomer having an acid group or the ammonium salt of a resin having an acid group is not particularly limited.
  • the ammonium salt of the monomer having an acid group or the ammonium salt of a resin having an acid group of the high refractive index transparent resin layer is preferably an acrylic monomer having an acid group or an ammonium salt of an acrylic resin.
  • the monomer having an acid group or the resin having an acid group is preferably a resin having an acid group.
  • the resin having an acid group is more preferably a resin having a monovalent acid group (such as a carboxyl group).
  • the binder polymer of the high refractive index transparent resin layer is particularly preferably a binder polymer having a carboxyl group.
  • a resin that is used for the high refractive index transparent resin layer and has solubility in an aqueous solvent preferably water or a mixed solvent of a lower alcohol having 1 to 3 carbon atoms and water
  • the resin having an acid group used for the high refractive index transparent resin layer is preferably an alkali-soluble resin.
  • the alkali-soluble resin is a linear organic polymer, and is a group that promotes at least one alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having an acid group (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. As the acid group, a carboxyl group is preferable.
  • a method using a known radical polymerization method can be applied.
  • Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. You can also
  • the polymer which has carboxylic acid in a side chain is preferable.
  • the polymer which has carboxylic acid in a side chain is preferable.
  • a polymer a maleic acid copolymer such as styrene / maleic acid, a partially esterified maleic acid copolymer, etc., an acidic cellulose derivative having a carboxylic acid in the side chain such as carboxyalkyl cellulose and carboxyalkyl starch, and a polymer having a hydroxyl group.
  • a maleic acid copolymer such as styrene / maleic acid, a partially esterified maleic acid copolymer, etc.
  • an acidic cellulose derivative having a carboxylic acid in the side chain such as carboxyalkyl cellulose and carboxyalkyl starch
  • a polymer having a hydroxyl group polymer having a hydroxyl group.
  • the resin having an acid group used for the high refractive index transparent resin layer is preferably an acrylic resin, and more preferably a carboxyl group-containing acrylic resin.
  • benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.
  • those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. This polymer can be used by mixing in an arbitrary amount.
  • 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Is mentioned.
  • a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable.
  • Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
  • the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
  • alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) ) Acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, cyclohexyl acrylate and the like.
  • copolymerizable monomers can be used singly or in combination of two or more.
  • Preferred other copolymerizable monomers are selected from CH 2 ⁇ CR 1 R 2 , CH 2 ⁇ C (R 1 ) (COOR 3 ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably CH 2 ⁇ CR 1 R 2 and / or CH 2 ⁇ C (R 1 ) (COOR 3 ).
  • a (meth) acrylic compound having a reactive functional group, cinnamic acid, or the like is allowed to react with a linear polymer having a substituent capable of reacting with the reactive functional group, thereby producing an ethylenically unsaturated double bond.
  • a resin in which is introduced into the linear polymer examples include a hydroxyl group, a carboxyl group, and an amino group.
  • the substituent capable of reacting with the reactive functional group include an isocyanate group, an aldehyde group, and an epoxy group.
  • the resin having an acid group is preferably an acrylic resin having an acid group.
  • acrylic resin includes both methacrylic resin and acrylic resin, and (meth) acrylic similarly includes methacrylic and acrylic.
  • acrylic monomers such as (meth) acrylic acid and derivatives thereof, and the following monomers can be preferably used.
  • a 5- to 6-functional radically polymerizable monomer di-acid
  • a bifunctional alkali-soluble radically polymerizable monomer may be used as necessary.
  • monomers having an acid group described in [0025] to [0030] of JP-A-2004-239842 can be preferably used, and the contents of this publication are incorporated in the present invention.
  • acrylic monomers such as (meth) acrylic acid and derivatives thereof can be used more preferably.
  • the acrylic monomer includes both a methacrylic monomer and an acrylic monomer.
  • binder polymer which does not have an acid group used for a high refractive index transparent resin layer
  • the binder polymer used for a transparent resin layer can be used.
  • the above-mentioned high refractive index transparent resin layer preferably contains a polymerizable compound such as the above-mentioned photopolymerizable compound or thermopolymerizable compound from the viewpoint of curing and increasing the strength of the film. It is more preferable to include other photopolymerizable compounds other than the aforementioned monomer having an acid group.
  • the photopolymerizable compound used in the high refractive index transparent resin layer the photopolymerizable compounds described in paragraphs 0023 to 0024 of Japanese Patent No. 4098550 can be used.
  • pentaerythritol tetraacrylate, pentaerythritol triacrylate, and tetraacrylate of pentaerythritol ethylene oxide adduct can be preferably used. These photopolymerizable compounds may be used alone or in combination.
  • pentaerythritol tetraacrylate and pentaerythritol triacrylate are used alone or in combination.
  • the ratio of pentaerythritol triacrylate to the total mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate is preferably 0 to 80% by mass. More preferably, it is ⁇ 60 mass%.
  • a photopolymerizable compound used for the high refractive index transparent resin layer specifically, a mixture of a water-soluble polymerizable compound represented by the following structural formula 1 and pentaerythritol tetraacrylate (NK ester A-TMMT Shin-Nakamura Chemical) Manufactured by Kogyo Co., Ltd., containing about 10% of triacrylate as an impurity), a mixture of pentaerythritol tetraacrylate and triacrylate (NK ester A-TMM3LM-N, Shin-Nakamura Chemical Co., Ltd., 37% triacrylate), pentaerythritol Mixture of tetraacrylate and triacrylate (NK Ester A-TMM-3L, Shin-Nakamura Chemical Co., Ltd., 55% triacrylate), Mixture of pentaerythritol tetraacrylate and triacrylate (NK Ester A-TMM3 Shin-Nakamura Chemical Co., Ltd
  • tetraacrylate of pentaerythritol ethylene oxide adduct (Kayarad RP-1040 manufactured by Nippon Kayaku Co., Ltd.), and the like.
  • a photopolymerizable compound used for the high refractive index transparent resin layer from the viewpoint of improving reticulation of a transfer film, a water-soluble polymerizable compound represented by the following structural formula 1, pentaerythritol Tetraacrylate mixture (NK ester A-TMMT, Shin-Nakamura Chemical Co., Ltd.), pentaerythritol tetraacrylate and triacrylate mixture (NK ester A-TMM3LM-N, Shin-Nakamura Chemical Co., Ltd., triacrylate 37%) Further, a mixture of pentaerythritol tetraacrylate and triacrylate (NK Ester A-TMM-3L, Shin-Nakamura Chemical Co., Ltd., triacrylate 55%) can be used as a photopoly
  • photopolymerizable compounds used for the high refractive index transparent resin layer as a polymerizable compound having solubility in water or a mixed solvent of lower alcohol having 1 to 3 carbon atoms and water, a hydroxyl group is used.
  • numerator can be used.
  • Photopolymerization initiator- IRGACURE 2959 or the following structural formula 2 is used as a photopolymerization initiator used in the above-described high refractive index transparent resin layer and having solubility in water or a mixed solvent of lower alcohol having 1 to 3 carbon atoms and water. Can be used.
  • the high refractive index transparent resin layer preferably contains a metal oxidation inhibitor.
  • the high refractive index transparent resin layer contains a metal oxidation inhibitor
  • the high refractive index transparent resin layer is laminated on a substrate (the substrate preferably includes a transparent electrode pattern and a metal wiring portion)
  • the substrate preferably includes a transparent electrode pattern and a metal wiring portion
  • the metal oxidation inhibitor is preferably a compound having an aromatic ring containing a nitrogen atom in the molecule.
  • the aromatic ring containing a nitrogen atom is at least selected from the group consisting of an imidazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, and a condensed ring of these and another aromatic ring.
  • One ring is preferred.
  • the metal oxidation inhibitor has an imidazole ring, a triazole ring, or a condensed ring of these with another aromatic ring in the molecule, and an imidazole ring, or an imidazole ring and another aromatic ring.
  • the other aromatic ring may be a monocyclic ring or a heterocyclic ring, but is preferably a monocyclic ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.
  • metal oxidation inhibitors include imidazole, benzimidazole, tetrazole, mercaptothiadiazole, and benzotriazole, and imidazole, benzimidazole, and benzotriazole are more preferable.
  • the content of the metal oxidation inhibitor is preferably 0.1 to 20% by mass, and preferably 0.5 to 10% by mass, based on the total mass of the solid content of the high refractive index transparent resin layer. More preferably, it is 1 to 5% by mass.
  • the high refractive index transparent resin layer described above may contain a surfactant containing fluorine atoms.
  • the surfactant containing a fluorine atom that can be used in the high refractive index transparent resin layer include surfactants containing a fluorine atom that can be used in the transparent resin layer.
  • the above-mentioned high refractive index transparent resin layer may or may not contain particles (preferably metal oxide particles) for the purpose of adjusting the refractive index and light transmittance.
  • the inclusion of particles is preferable from the viewpoint of controlling the refractive index of the high refractive index transparent resin layer within the above range.
  • the above-described high refractive index transparent resin layer can contain metal oxide particles at an arbitrary ratio depending on the type of polymer or polymerizable compound (preferably photopolymerizable compound) to be used.
  • the refractive index of the aforementioned metal oxide particles is preferably higher than the refractive index refractive index of the high refractive index transparent resin layer not including the metal oxide particles.
  • the above-described metal oxide particles preferably have a refractive index higher than that of a composition made of a material obtained by removing the particles from the high refractive index transparent resin layer.
  • the high refractive index transparent resin layer contains particles having a refractive index of 1.50 or more in light having a wavelength of 400 to 750 nm. It is further preferable to contain 70 or more particles, particularly preferably 1.90 or more particles, and more preferably 2.00 or more particles.
  • the light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb.
  • Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable, such as titanium oxide, titanium composite oxide, zinc oxide, and zirconium oxide. More preferred are metal oxides containing zirconium atoms, indium / tin oxide and antimony / tin oxide, more preferred are titanium oxide, titanium composite oxide and zirconium oxide, and particularly preferred are titanium oxide and zirconium oxide.
  • Titanium oxide is particularly preferably a rutile type having a high refractive index.
  • the metal oxide containing a zirconium atom is preferably a composite of zirconium oxide and tin oxide. Examples of the tin oxide and the composite of zirconium oxide and tin oxide are described in [0027] to [0078] of JP-A-2005-15756 and [0026] to [0073] of JP-A-2005-15324. The contents of these publications are incorporated herein.
  • the surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.
  • the refractive index of light having a wavelength of 400 to 750 nm being 1.50 or more means that the average refractive index of light having a wavelength in the above range is 1.50 or more. It is not necessary that the refractive index of all light having a wavelength is 1.50 or more.
  • an average refractive index is an average value of the refractive index with respect to the light of each wavelength of the said range.
  • the average primary particle diameter of the metal oxide particles is preferably 1 to 200 nm, particularly preferably 3 to 80 nm.
  • the average primary particle diameter of the particles refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the longest side is the diameter.
  • the metal oxide particles described above may be used alone or in combination of two or more.
  • the high refractive index transparent resin layer has at least one of ZrO 2 particles, Nb 2 O 5 particles, and TiO 2 particles, and the refractive index range of the high refractive index transparent resin layer described above. From the viewpoint of controlling the refractive index, ZrO 2 particles and Nb 2 O 5 particles are more preferable.
  • Examples of the metal oxide containing a zirconium atom that can be used in the present invention include nano-use OZ-S30M (zirconium oxide and tin oxide-containing inorganic particles, ie, a composite of zirconium oxide and tin oxide) manufactured by Nissan Chemical Industries, Nissan Nano-use ZR-30BS (yttria-containing zirconium oxide particles) manufactured by Chemical Industry Co., Ltd. can be exemplified.
  • the transfer film of the present invention has a viewpoint of improving the concealability of the transparent electrode pattern when the high refractive index transparent resin layer contains 40% by mass or more of metal oxide particles in a solid content ratio when laminated on the transparent electrode pattern. From 40 to 95% by mass, more preferably from 55 to 95% by mass, particularly preferably from 62 to 90% by mass from the viewpoint of improving cracking of the transfer film, from 62 to 90% by mass. The content of 75% by mass is particularly preferable from the viewpoints of further improving cracking of the transfer film and improving the substrate adhesion of the laminate of the present invention.
  • the high refractive index transparent resin layer preferably has at least one of ZrO 2 particles and TiO 2 particles.
  • the high refractive index transparent resin layer preferably contains 40 to 95% by mass of metal oxide particles, more preferably 55 to 95% by mass, and 62 to 90% by mass. % Is particularly preferable, and 62 to 75% by mass is more particularly preferable.
  • the metal oxide particles are titanium oxide
  • the high refractive index transparent resin layer preferably contains 30 to 70% by mass of metal oxide particles.
  • the proportion of the area occupied by the metal oxide particles in the film cross-sectional area of the high refractive index transparent resin layer (or transparent resin layer) is measured at any three locations in the layer, and the average value is the volume fraction (VR).
  • the volume fraction (VR) and the weight fraction (WR) are converted by the following formula to obtain the weight fraction (WR) of the metal oxide particles in the high refractive index transparent resin layer (or transparent resin layer). calculate.
  • WR D * VR / (1.1 * (1-VR) + D * VR)
  • D Specific gravity of metal oxide particles
  • thermoplastic resin layer In the transfer film of the present invention, a thermoplastic resin layer can be provided between the temporary support and the transparent resin layer.
  • a laminate is formed by transferring a transparent resin layer and a high refractive index transparent resin layer using the transfer film having the thermoplastic resin layer described above, bubbles are less likely to be generated in each layer formed by transfer, and image display Image unevenness or the like hardly occurs in the apparatus, and excellent display characteristics can be obtained.
  • the thermoplastic resin layer described above is preferably alkali-soluble.
  • the thermoplastic resin layer plays a role as a cushioning material so as to be able to absorb unevenness of the underlying surface (for example, unevenness of an electrode pattern, including unevenness caused by an already formed image, etc.). It is preferable that it has a property that can be deformed according to the unevenness of the underlying surface.
  • the thermoplastic resin layer preferably includes an organic polymer substance described in JP-A-5-72724 as a component, and is based on the Vicat method [specifically, based on American Material Testing Method ASTM D1235.
  • polyolefins such as polyethylene and polypropylene, ethylene copolymers with ethylene and vinyl acetate or saponified products thereof, copolymers of ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride and vinyl chloride, Vinyl chloride copolymer with vinyl acetate or saponified product thereof, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer with styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyltoluene , Vinyl toluene copolymer of vinyl toluene and (meth) acrylic acid ester or saponified product thereof, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer of butyl (meth) acrylate and vinyl acetate, etc. Polymer, vinyl acetate copolymer nylon, copolymer Niro
  • the thickness of the thermoplastic resin layer is preferably 3 to 30 ⁇ m.
  • the thickness of the thermoplastic resin layer is more preferably 4 to 25 ⁇ m, and particularly preferably 5 to 20 ⁇ m.
  • the thermoplastic resin layer can be formed by applying a preparation liquid containing a thermoplastic organic polymer, and the preparation liquid used for the application can be prepared using a solvent.
  • the solvent is not particularly limited as long as it can dissolve the polymer component constituting the thermoplastic resin layer, and examples thereof include methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, and 2-propanol.
  • thermoplastic resin layer preferably has a viscosity measured at 100 ° C. in the range of 1000 to 10,000 Pa ⁇ s.
  • an intermediate layer can be provided between the thermoplastic resin layer and the transparent resin layer.
  • the intermediate layer is preferably a layer described as “separation layer” in JP-A-5-72724.
  • the transfer film of the present invention preferably further includes a protective film (hereinafter also referred to as “protective release layer”) or the like on the surface of the above-described high refractive index transparent resin layer.
  • a protective film hereinafter also referred to as “protective release layer” or the like on the surface of the above-described high refractive index transparent resin layer.
  • protective films described in paragraphs 0083 to 0087 and 0093 of JP-A-2006-259138 can be appropriately used.
  • FIG. 12 shows an example of a preferred configuration of the transfer film of the present invention.
  • FIG. 12 shows an outline of the transfer film 30 of the present invention in which the temporary support 26, the transparent resin layer 7, the high refractive index transparent resin layer 12, and the protective release layer (protective film) 29 are laminated adjacent to each other in this order.
  • FIG. 12 shows an outline of the transfer film 30 of the present invention in which the temporary support 26, the transparent resin layer 7, the high refractive index transparent resin layer 12, and the protective release layer (protective film) 29 are laminated adjacent to each other in this order.
  • the transfer film manufacturing method includes the step of forming the transparent resin layer on the temporary support, and And forming a high refractive index transparent resin layer directly on the transparent resin layer.
  • the step of forming the transparent resin layer is preferably a step of applying the organic solvent-based resin composition onto the temporary support. Since the second resin layer obtained using the water-based resin composition is easily dissolved in water, it is preferable that the second resin layer has a composition that hardly causes the problem of wet heat durability of the transfer film.
  • the step of forming the high refractive index transparent resin layer is preferably a step of applying the aqueous resin composition. More preferably, the step of forming the high refractive index transparent resin layer is a step of applying an aqueous resin composition containing an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group.
  • the layer fraction is good, and the problem caused by moisture absorption of the transparent resin layer formed using the aqueous resin composition can be suppressed when aged at high temperature and high humidity. .
  • an aqueous resin composition containing an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group on the transparent resin layer obtained by the organic solvent-based resin composition, Even if the high refractive index transparent resin layer is formed without being cured, layer mixing does not occur and the layer fraction is improved. Further, when drying a coating film obtained using an aqueous resin composition containing an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group, the ammonium salt or acid group of the monomer having an acid group is dried.
  • Ammonia which has a lower boiling point than water, easily volatilizes in the drying process from an ammonium salt of a resin having a high refractive index as a monomer having an acid group or a resin having an acid group by generating (regenerating) an acid group Can be present in the layer. For this reason, when the moisture is absorbed over time under high temperature and high humidity, the monomer having an acid group or the resin having an acid group constituting the high refractive index transparent resin layer is no longer dissolved in water. It is also possible to suppress problems when doing so.
  • the method for producing a transfer film has a step of forming a transparent resin layer on a temporary support, and the step of forming the transparent resin layer applies an organic solvent-based resin composition on the temporary support. It is preferable that it is a process.
  • the organic solvent-based resin composition refers to a resin composition that can be dissolved in an organic solvent.
  • a common organic solvent can be used as the organic solvent.
  • the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.
  • the organic solvent-based resin composition used for forming the transparent resin layer preferably contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator.
  • the method has a step of directly forming a high refractive index transparent resin layer on the transparent resin layer, and the step of forming the above high refractive index transparent resin layer comprises an ammonium salt of a monomer having an acid group. Or it is preferable that it is the process of apply
  • the aqueous resin composition refers to a resin composition that can be dissolved in an aqueous solvent.
  • the aqueous solvent water or a mixed solvent of lower alcohol having 1 to 3 carbon atoms and water is preferable.
  • the solvent of the aqueous resin composition used for forming the high refractive index transparent resin layer preferably contains water and an alcohol having 1 to 3 carbon atoms, and water / carbon atom is 1 More preferably, it contains water or a mixed solvent having an alcohol content of ⁇ 3 in a mass ratio of 58 / 42 ⁇ 100 / 0.
  • the content of water / alcohol having 1 to 3 carbon atoms is particularly preferably 59/41 to 100/0 in terms of mass ratio, and 60/40 to 97/3 is from the viewpoint of improving the coloration of the laminate of the present invention. More particularly preferred is 62/38 to 95/5, still more preferred from the viewpoint of improving the substrate adhesion of the laminate of the present invention, and most preferred is 62/38 to 85/15.
  • a mixed solvent of water, water and methanol, and a mixed solvent of water and ethanol are preferable, and a mixed solvent of water and methanol is more preferable from the viewpoint of drying and coating properties.
  • the water / methanol mass ratio is preferably 58/42 to 100/0, The range of 41 to 100/0 is more preferred, 60/40 to 97/3 is particularly preferred, 62/38 to 95/5 is more particularly preferred, and 62/38 to 85/15 is even more particularly preferred.
  • the content of water / alcohol having 1 to 3 alcohols is less than the mass ratio of 58/42, the transparent resin layer is difficult to dissolve and white turbid, which is preferable.
  • the aqueous resin composition has a pH (Power of Hydrogen) at 25 ° C. of preferably 7.0 or more and 12.0 or less, more preferably 7.0 to 10.0, and more preferably 7.0 to 8. 5 is particularly preferred.
  • a pH Power of Hydrogen
  • an excess amount of ammonia with respect to the acid group can be used, and a monomer having an acid group or a resin having an acid group can be added to adjust the pH of the aqueous resin composition to the above preferred range.
  • the water-system resin composition used for formation of a high refractive index transparent resin layer is at least one among thermosetting and photocurability.
  • the transparent resin layer and the high refractive index transparent resin layer are curable transparent resin layers, according to the method for producing a transfer film, even if the high refractive index transparent resin layer is laminated without being cured after the transparent resin layer is laminated, The layer fraction is improved and the transparent electrode pattern concealing property can be improved.
  • the transparent laminate described later is further transferred by photolithography after the refractive index adjusting layer (that is, the transparent resin layer and the high refractive index transparent resin layer) is simultaneously transferred from the obtained transfer film onto the transparent electrode pattern. At least the transparent resin layer that is closer to the outside than the high refractive index transparent resin layer after transfer can be developed into a desired pattern.
  • An embodiment in which the second transparent resin layer has curability is more preferable.
  • the aqueous resin composition used for forming the high refractive index transparent resin layer has an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group, a binder polymer, Or it is preferable that a thermopolymerizable compound and light or a thermal-polymerization initiator are included. Only the ammonium salt of the resin having an acid group may be a binder polymer, or in addition to the ammonium salt of a resin having an acid group, another binder polymer may be used in combination. The ammonium salt of the monomer having an acid group may be a photo or thermopolymerizable compound, and in addition to the ammonium salt of the monomer having an acid group, a photo or thermopolymerizable compound may be used in combination.
  • the method for producing a transfer film preferably includes a step of generating an acid group by volatilizing ammonia from an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group.
  • the step of generating an acid group by volatilizing ammonia from the ammonium salt of the monomer having an acid group or the ammonium salt of a resin having an acid group is a step of heating the applied aqueous resin composition.
  • a heating and drying method it can be carried out by passing through a furnace equipped with a heating device, or by blowing air.
  • the heating and drying conditions may be appropriately set according to the organic solvent used, and examples thereof include a method of heating to a temperature of 40 to 150 ° C. Among these conditions, heating at a temperature of 50 to 120 ° C is particularly preferable, and heating to a temperature of 60 to 100 ° C is more preferable.
  • the moisture content on a wet basis is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less.
  • thermoplastic resin layer Before forming the above-mentioned transparent resin layer on the above-mentioned temporary support, you may include the process of forming a thermoplastic resin layer further.
  • a step of forming an intermediate layer between the thermoplastic resin layer and the transparent resin layer may be included.
  • a solution addition liquid for thermoplastic resin layer
  • a prepared solution prepared by adding a resin or an additive to a solvent that does not dissolve the thermoplastic resin layer is applied onto this thermoplastic resin layer and dried. It is preferable to laminate the intermediate layer. It is preferable that a transparent resin layer coating solution prepared using a solvent that does not dissolve the intermediate layer is further applied on the intermediate layer and dried to laminate the transparent resin layer.
  • the method for producing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138 can be employed.
  • the transfer film of the present invention is preferably a dry resist film.
  • the dry resist refers to a product in which a transfer film takes a film form.
  • the transparent resin layer and the high refractive index transparent resin layer preferably have curability from the viewpoint of photolithography.
  • the transfer film of the present invention is preferably for a transparent insulating layer or a transparent protective layer of a capacitive input device. More specifically, the transfer film of the present invention is preferably used as a transfer film for forming a laminated pattern of a refractive index adjusting layer and an overcoat layer (transparent protective layer) on a transparent electrode pattern by a photolithography method. Can do.
  • the transfer film of the present invention is preferably used for a protective film for an electrode of a capacitive input device. The protective film for electrodes of the capacitive input device is obtained by removing the temporary support from the transfer film of the present invention.
  • the laminate of the present invention comprises an electrode pattern, A high refractive index transparent resin layer disposed adjacent to the electrode pattern; A transparent resin layer disposed adjacent to the high refractive index transparent resin layer, The refractive index of the high refractive index transparent resin layer is higher than the refractive index of the transparent resin layer, High refractive index transparent resin layer and transparent resin layer are patterned, A laminated body having an undercut depth of 5.0 ⁇ m or less at a pattern end of two layers comprising a high refractive index transparent resin layer and a transparent resin layer; However, the undercut depth of the pattern end of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer is an upper portion (more than half of the total film thickness of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer) Parallel to the interface between the high refractive index transparent resin layer and the electrode pattern at the distance between the pattern extreme end point at the half and the upper half) and the contact point between the pattern edge of the high refractive index transparent
  • the undercut depth at the pattern end of the two layers comprising the high refractive index transparent resin layer and the transparent resin layer is 5.0 ⁇ m or less.
  • the “undercut depth of the pattern end of the two layers comprising the high refractive index transparent resin layer and the transparent resin layer” as referred to in the present invention is half of the total film thickness of the two layers comprising the high refractive index transparent resin layer and the transparent resin layer.
  • the distance between the pattern uppermost point (the side far from the electrode pattern) and the contact point between the pattern edge of the high refractive index transparent resin layer and the electrode pattern is “parallel to the interface between the high refractive index transparent resin layer and the electrode pattern
  • the value of the component in the “direction” (horizontal distance) (refer to FIG. 16).
  • the above-mentioned “undercut depth” used in the present invention generally corresponds to a value called an undercut depth in the field of photolithography.
  • the electrode pattern often has a different layer structure depending on the location and has a different height (for example, the right side is higher by the thickness of the routing wiring 6 than the left side in FIG. 16).
  • the “electrode pattern interface” is defined between each pattern edge and the layer in contact with the high refractive index transparent resin layer in the vicinity thereof (for example, the left pattern edge in FIG. 16 has a high refractive index transparent resin layer 12).
  • the interface between the transparent film 11 and the transparent film 11 is “the interface between the high-refractive-index transparent resin layer and the electrode pattern”, and the interface between the high-refractive-index transparent resin layer 12 and the wiring 6 is “high-refractive-index transparent resin layer” And electrode pattern interface ”).
  • An example of the laminated body of the present invention is described on the right side of the opening 34 corresponding to the terminal portion of the routing wiring in FIG. 16, and the example of the laminated body of the present invention shown in FIG.
  • Another conductive element 6) that is a lead-out wiring, a high refractive index transparent resin layer 12 disposed adjacent to the electrode pattern, and a transparent resin layer 7 disposed adjacent to the high refractive index transparent resin layer 12 Have
  • One example of the laminate of the present invention described in FIG. 16 has a patterned transparent resin layer and a high refractive index transparent resin layer 33, and is composed of two layers (members) consisting of a high refractive index transparent resin layer and a transparent resin layer. 35)
  • the undercut depth U at the pattern edge is 5.0 ⁇ m or less.
  • the undercut depth U of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer is not less than half of the total film thickness H of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer.
  • a direction parallel to the interface between the high refractive index transparent resin layer and the electrode pattern at a distance between the pattern endmost point E on the upper side (the side far from the electrode pattern) and the contact point F between the pattern end of the high refractive index transparent resin layer and the electrode pattern The value of the component (horizontal distance), that is, the value indicated by “U”.
  • the upper part of more than half of the total film thickness H of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer means “H” in FIG.
  • the contact point F between the pattern edge of the high refractive index transparent resin layer and the electrode pattern is the uppermost pattern at least half of the total film thickness H of the two layers of the high refractive index transparent resin layer and the transparent resin layer.
  • the undercut depth U assumes a positive value.
  • the contact point F between the pattern end of the high refractive index transparent resin layer and the electrode pattern is the uppermost pattern end point of more than half of the total film thickness H of the two layers consisting of the high refractive index transparent resin layer and the transparent resin layer.
  • FIG. 17 is a schematic view showing an example of a cross section of the laminate of the present invention.
  • FIG. 17 (A) shows an embodiment of an undercut depth U> 0, and
  • FIG. 17C shows an embodiment where the undercut depth U ⁇ 0.
  • the undercut depth at the pattern end of the two layers comprising the high refractive index transparent resin layer and the transparent resin layer is preferably 4 ⁇ m or less, more preferably 3 ⁇ m or less, and less than 0 ⁇ m. It is particularly preferred. Further, from the viewpoint of pattern resolution, it is preferably ⁇ 100 ⁇ m or more.
  • patterning with a cutting method using a blade such as a die cut instead of patterning with a photolithography method will result in a high refractive index transparent resin layer and a transparent resin layer.
  • the undercut depth at the pattern edge of the two layers is not less than 0 ⁇ m.
  • the laminate of the present invention has an electrode pattern, a high refractive index transparent resin layer disposed adjacent to the electrode pattern, and a transparent resin layer disposed adjacent to the high refractive index transparent resin layer.
  • the electrode pattern is preferably an electrode pattern of a capacitive input device, and more preferably a transparent electrode pattern of the capacitive input device or a lead wiring of the capacitive input device. Since the extraction wiring such as a copper electrode often exists on a transparent electrode pattern such as ITO at the pattern end, it is more preferable that the electrode pattern is a routing wiring of the capacitive input device.
  • the laminate of the present invention has a high refractive index transparent resin layer disposed adjacent to the transparent electrode pattern of the capacitive input device in a region where the electrode pattern that is the routing wiring does not exist in the plane, and a high It is also preferable to have a transparent resin layer disposed adjacent to the refractive index transparent resin layer.
  • the laminate of the present invention has a refractive index of 1.6 to 1.78 and a film thickness of 55 to 110 nm on the side of the electrode pattern opposite to the side on which the high refractive index transparent resin layer is formed. It is preferable to further have a film from the viewpoint of further improving the concealability of the transparent electrode pattern.
  • transparent film refers to the above “transparent film having a refractive index of 1.6 to 1.78 and a film thickness of 55 to 110 nm” unless otherwise specified.
  • the laminate of the present invention further has a substrate on the opposite side of the transparent film having the refractive index of 1.6 to 1.78 and the film thickness of 55 to 110 nm on which the transparent electrode pattern is formed. It is preferable.
  • FIG. 11 shows an example of the configuration of the laminate of the present invention.
  • the laminate 13 of the present invention has a substrate 1, a transparent film 11 having a refractive index of 1.6 to 1.78 and a film thickness of 55 to 110 nm, a transparent electrode pattern 4, a high refractive index.
  • the surface 21 has a region 21 in which the transparent resin layer 12 and the transparent resin layer 7 are laminated in this order.
  • the above-described laminated body is a region in which the substrate 1 and the transparent film 11 are laminated in this order (in the configuration of FIG. 11, the high refractive index transparent resin layer 12 and the transparent resin layer).
  • the transparent laminated body described above includes the region 21 in which the substrate 1, the transparent film 11, the transparent electrode pattern 4, the high refractive index transparent resin layer 12 and the transparent resin layer 7 are laminated in this order in the in-plane direction.
  • the in-plane direction means a direction substantially parallel to a plane parallel to the substrate of the laminate. Therefore, the transparent electrode pattern 4, the high refractive index transparent resin layer 12, and the transparent resin layer 7 include in the plane a region where the transparent electrode pattern 4, the high refractive index transparent resin layer 12 and the transparent resin layer 7 are laminated in this order.
  • the transparent electrode pattern has a first transparent electrode pattern and a second transparent electrode in two directions substantially orthogonal to the row direction and the column direction, respectively. It may be provided as an electrode pattern (see, for example, FIG. 3).
  • the transparent electrode pattern in the laminate of the present invention may be the second transparent electrode pattern 4 or the pad portion 3 a of the first transparent electrode pattern 3.
  • the reference numeral of the transparent electrode pattern may be represented by “4”.
  • the transparent electrode pattern in the laminate of the present invention is not limited to use for the second transparent electrode pattern 4 in the capacitive input device of the present invention, and is used as, for example, the pad portion 3a of the first transparent electrode pattern 3. May be.
  • the laminated body of this invention contains the non-pattern area
  • the non-pattern region means a region where the transparent electrode pattern 4 is not formed.
  • FIG. 11 shows a mode in which the laminate of the present invention includes a non-pattern region 22.
  • the substrate, the transparent film, and the high refractive index transparent resin layer are stacked in this order on at least a part of the non-pattern region 22 where the transparent electrode pattern is not formed.
  • the region is preferably included in the plane.
  • the transparent film and the high refractive index transparent resin layer are adjacent to each other in a region where the substrate, the transparent film, and the high refractive index transparent resin layer are stacked in this order. It is preferable. However, in the other areas of the non-pattern area 22 described above, other members may be disposed at arbitrary positions as long as they do not contradict the spirit of the present invention.
  • the mask layer 2 in FIG. 1A, the insulating layer 5, another conductive element 6 and the like can be laminated.
  • FIG. 11 shows a mode in which the above-described transparent film 11 is laminated adjacently on the above-described substrate 1.
  • a third transparent film may be laminated between the aforementioned substrate and the aforementioned transparent film as long as it does not contradict the gist of the present invention.
  • the thickness of the transparent film is preferably 55 to 110 nm, more preferably 60 to 110 nm, and particularly preferably 70 to 90 nm.
  • the transparent film described above may have a single layer structure or a laminated structure of two or more layers.
  • the thickness of the transparent film means the total thickness of all layers.
  • FIG. 11 shows an aspect in which the transparent electrode pattern 4 is laminated adjacently on a partial region of the transparent film 11.
  • the end of the transparent electrode pattern 4 is not particularly limited in shape, and may have a tapered shape as shown in FIG. It may have a taper shape wider than the surface on the opposite side.
  • the angle of the end of the transparent electrode pattern (hereinafter also referred to as a taper angle) is preferably 30 ° or less, 0.1 to 15 More preferably, the angle is more preferably 0.5 to 5 °.
  • the method for measuring the taper angle in this specification can be obtained by taking a photomicrograph of the end of the transparent electrode pattern described above, approximating the taper portion of the photomicrograph to a triangle, and directly measuring the taper angle. .
  • FIG. 10 shows an example in which the end portion of the transparent electrode pattern is tapered.
  • the triangle that approximates the tapered portion in FIG. 10 has a bottom surface of 800 nm and a height (thickness at the upper base portion substantially parallel to the bottom surface) of 40 nm, and the taper angle ⁇ at this time is about 3 °.
  • the bottom surface of the triangle that approximates the tapered portion is preferably 10 to 3000 nm, more preferably 100 to 1500 nm, and particularly preferably 300 to 1000 nm.
  • the preferable range of the height of the triangle which approximated the taper part is the same as the preferable range of the thickness of the transparent electrode pattern.
  • the laminate of the present invention preferably includes a region in which the transparent electrode pattern and the high refractive index transparent resin layer are adjacent to each other.
  • FIG. 11 shows the above-mentioned transparent electrode pattern, the above-described high refractive index transparent resin layer, and the transparent resin in the region 21 in which the above-described transparent electrode pattern, the above-described high refractive index transparent resin layer, and the transparent resin layer are laminated in this order.
  • An embodiment is shown in which the layers are adjacent to each other.
  • both the transparent electrode pattern and the non-pattern region 22 where the transparent electrode pattern is not formed are continuously formed by the transparent film and the high refractive index transparent resin layer. It is preferably coated directly or via other layers.
  • “continuously” means that the transparent film and the high refractive index transparent resin layer described above are not a pattern film but a continuous film. That is, it is preferable that the above-described transparent film and the above-described high refractive index transparent resin layer have no opening from the viewpoint of making the transparent electrode pattern difficult to be visually recognized. Further, it is preferable that the transparent electrode pattern and the non-pattern region 22 are directly covered with the transparent film and the high refractive index transparent resin layer, rather than being covered with another layer. .
  • FIG. 11 shows an aspect in which the above-described high refractive index transparent resin layer 12 is laminated.
  • the above-described high refractive index transparent resin layer 12 is laminated over a region where the transparent electrode pattern 4 on the transparent film 11 is not laminated and a region where the transparent electrode pattern 4 is laminated. .
  • the high refractive index transparent resin layer 12 is adjacent to the transparent film 11, and the high refractive index transparent resin layer 12 is adjacent to the transparent electrode pattern 4. Moreover, when the edge part of the transparent electrode pattern 4 is a taper shape, it is preferable that the above-mentioned high refractive index transparent resin layer 12 is laminated
  • FIG. 11 shows an aspect in which the transparent resin layer 7 is laminated on the surface of the high refractive index transparent resin layer 12 on the side opposite to the surface on which the transparent electrode pattern is formed. Yes.
  • the substrate is preferably a glass substrate or a film substrate.
  • the substrate is preferably a transparent substrate.
  • the electrode pattern is preferably an electrode pattern formed on a transparent film substrate. That is, the above-mentioned substrate is preferably a transparent film substrate.
  • the refractive index of the aforementioned substrate is particularly preferably 1.5 to 1.52.
  • the above-mentioned substrate may be composed of a light-transmitting substrate such as a glass substrate, and tempered glass represented by Corning's gorilla glass can be used.
  • the above-mentioned transparent substrate materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.
  • a film substrate is used as the aforementioned substrate, it is more preferable to use a substrate that is not optically distorted or that has high transparency.
  • the film substrate include a film substrate containing polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and a cycloolefin polymer.
  • PET polyethylene terephthalate
  • the laminated body of this invention has an electrode pattern, a high refractive index transparent resin layer, and a transparent resin layer on both surfaces of a transparent film substrate, respectively.
  • FIG. 9 is a schematic cross-sectional view showing a preferred configuration of a capacitive input device that is a front plate integrated sensor using a film sensor.
  • the capacitance type input device which is a front plate integrated sensor includes a substrate 1 used as a front plate, a mask layer (second decorating layer) 2, a film sensor 43, and an adhesive material 51. The embodiment being shown is shown.
  • two layers 35 each including a transparent electrode pattern 3 or 4, a high refractive index transparent resin layer, and a transparent resin layer are provided on both surfaces of a base sheet 1 A corresponding to a transparent film substrate.
  • the film sensor 43 shown in FIG. 9 includes an electrode pattern 4, a light-shielding conductive film 9, a transparent resin layer, and a high-refractive-index transparent resin layer on the surface of the base sheet 1A on the side laminated with the substrate.
  • the two layers 35, the routing wiring 6, and the decoration layer 45 are arranged.
  • the film sensor of FIG. 9 has an electrode pattern 3, a light-shielding conductive film 9, a transparent resin layer, and a high refractive index transparent resin layer on the surface of the base sheet 1A opposite to the side laminated with the substrate.
  • the two layers 35 and the routing wiring 6 are arranged.
  • the film sensor preferably has a decorative layer 45 (a decorative layer of the film sensor). Even when laminating a colored composition layer across the lead wiring 6 and the overcoat layer that require a certain thickness, it is possible to use a transfer film in a simple process without using expensive equipment such as a vacuum laminator. Lamination with no generation of bubbles at the boundary of the mask portion is possible.
  • the decorative layer is preferably a frame-shaped decorative layer. That is, when a film sensor is used in an image display device having a front plate integrated sensor, which will be described later, as a constituent element, the decorative layer surrounds the central image display portion (electronic device display window) in a frame shape. preferable.
  • the same aspect as the frame-shaped light shielding layer described in Japanese Patent No. 5020580 can be exemplified.
  • the refractive index of the transparent electrode pattern is preferably 1.75 to 2.1.
  • the material for the transparent electrode pattern is not particularly limited, and a known material can be used. For example, it can be manufactured using a light-transmitting conductive metal oxide film such as ITO or IZO, or a metal film. Examples of the metal oxide film and the metal film include an ITO film; a metal film such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; and a metal oxide film such as SiO 2 . At this time, the thickness of each element can be set to 10 to 200 nm. Further, since the amorphous ITO film is made into a polycrystalline ITO film by firing, the electrical resistance can be reduced.
  • the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 described later are photosensitive having a conductive photocurable resin layer using conductive fibers. It can also be produced using a film.
  • the transparent electrode pattern described above is preferably an ITO film.
  • the transparent electrode pattern is preferably an ITO film having a refractive index of 1.75 to 2.1.
  • the preferable ranges of the transparent resin layer and the high refractive index transparent resin layer contained in the laminate of the present invention are the same as the preferable ranges of the above transparent resin layer and the above high refractive index transparent resin layer in the transfer film of the present invention.
  • the laminate of the present invention preferably has a C / H ratio of 0.68 or more, which is a ratio of carbon and hydrogen in the mass of the transparent resin layer.
  • the high refractive index transparent resin layer preferably contains a metal oxidation inhibitor, and the metal oxidation inhibitor has an imidazole ring, a triazole ring or a condensed ring of these and other aromatic rings in the molecule. It is more preferable to have.
  • the high refractive index transparent resin layer preferably contains 40% by mass or more of metal oxide particles in a solid content ratio, and the amount of metal oxide particles contained in the high refractive index transparent resin layer is preferred. The range is the same as the preferable range of the amount of metal oxide particles contained in the high refractive index transparent resin layer of the transfer film of the present invention.
  • the refractive index of the transparent film is preferably 1.6 to 1.78, more preferably 1.65 to 1.74.
  • the transparent film described above may have a single layer structure or a laminated structure of two or more layers.
  • the refractive index of the aforementioned transparent film means the refractive index of all layers. It is preferable to satisfy the refractive index range, but the material of the transparent film is not particularly limited.
  • the preferred range of the material for the transparent film and the preferred range for the physical properties such as the refractive index are the same as those for the high refractive index transparent resin layer.
  • the above-described transparent film and the above-described high refractive index transparent resin layer are preferably composed of the same material from the viewpoint of optical homogeneity.
  • the transparent film is preferably a transparent resin film.
  • the metal oxide particles, resin (binder) and other additives used for the transparent resin film are not particularly limited as long as they do not contradict the gist of the present invention, and the above-described high refractive index transparent resin layer in the transfer film of the present invention. Resins and other additives used in the above can be preferably used.
  • the transparent film may be an inorganic film.
  • the refractive index of the third transparent film described above is preferably 1.5 to 1.55 from the viewpoint of improving the concealing property of the transparent electrode pattern because it approaches the refractive index of the substrate described above. More preferably, it is 1.52.
  • the laminate of the present invention is preferably produced by laminating the high refractive index transparent resin layer and the transparent resin layer of the transfer film of the present invention in this order on the electrode pattern. It is more preferable to include a step of transferring the high refractive index transparent resin layer and the transparent resin layer of the transfer film of the present invention onto the substrate including the electrode pattern of the capacitive input device using the transfer film of the present invention.
  • the manufacturing method of a laminated body includes the process of laminating
  • the high refractive index transparent resin layer of the laminate and the above-described transparent resin layer can be collectively transferred, and a laminate having no problem of visually recognizing the transparent electrode pattern is easily produced with high productivity. be able to.
  • the above-mentioned high refractive index transparent resin layer is formed on the above-mentioned transparent electrode pattern and on the above-mentioned transparent film in the above-mentioned non-pattern area
  • an input means such as a finger is used in advance on the non-contact surface of the substrate (the surface of the substrate constituting the capacitive input device).
  • Surface treatment can be performed on the surface opposite to the surface to be contacted.
  • a surface treatment silane coupling treatment
  • silane coupling agent those having a functional group that interacts with the photosensitive resin are preferable.
  • a pure water shower is sprayed with a silane coupling solution (0.3 mass% aqueous solution of N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) for 20 seconds. Wash. Thereafter, the reaction is carried out by heating. A heating tank may be used, and the reaction can be promoted by preheating the substrate of the laminator.
  • a silane coupling solution 0.3 mass% aqueous solution of N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.
  • the above-mentioned transparent electrode pattern uses the method of forming the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 in the description of the capacitive input device of the present invention described later.
  • a film on a substrate or a transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm it is possible to form a film on a substrate or a transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm, and a method using a photosensitive film described later is preferable.
  • the method for forming the above-mentioned transparent resin layer and the above-described high refractive index transparent resin layer includes a protective film removing step for removing the above-mentioned protective film from the transfer film of the present invention, and a method for removing the above-mentioned protective film from the present invention.
  • the above-mentioned transfer step is preferably a step of transferring the above-mentioned transparent resin layer and the above-mentioned high refractive index transparent resin layer of the transfer film of the present invention from which the above-mentioned protective film has been removed onto a transparent electrode pattern.
  • the method of including the process of removing the base material (temporary support body) after laminating the above-mentioned transparent resin layer and the above-mentioned high refractive index transparent resin layer of the transfer film of this invention on a transparent electrode pattern is preferable.
  • Transfer (bonding) of the transparent resin layer and the high refractive index transparent resin layer to the transparent electrode pattern surface is performed by superimposing the transparent resin layer and the high refractive index transparent resin layer on the transparent electrode pattern surface, This is done by applying pressure and heating.
  • laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
  • the exposure process is a process of exposing the transparent resin layer and the high refractive index transparent resin layer transferred onto the transparent electrode pattern.
  • a predetermined mask is disposed above the transparent resin layer and the high refractive index transparent resin layer formed on the transparent electrode pattern and the temporary support, and then a light source above the mask ( And a method of exposing the aforementioned transparent resin layer and the aforementioned high refractive index transparent resin layer (via a mask and a temporary support).
  • the light source for the exposure is appropriately selected as long as it can irradiate light (for example, 365 nm, 405 nm, etc.) in a wavelength region capable of curing the transparent resin layer and the high refractive index transparent resin layer.
  • an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned.
  • the exposure amount is usually about 5 to 200 mJ / cm 2 , preferably about 10 to 100 mJ / cm 2 .
  • the aforementioned developing step is a step of developing the exposed transparent resin layer and high refractive index transparent resin layer.
  • the above-described development step is a development step in a narrow sense that pattern-develops the pattern-exposed transparent resin layer and the high refractive index transparent resin layer with a developer.
  • the development described above can be performed using a developer.
  • the developer is not particularly limited, and a known developer such as the developer described in JP-A-5-72724 can be used.
  • the developing solution is preferably a developing solution in which the photocurable resin layer has a dissolution type developing behavior.
  • a compound having pKa power of Ka; Ka is an acid dissociation constant
  • Ka is an acid dissociation constant
  • a developer containing a concentration of L is preferred.
  • the developer in the case where the transparent resin layer and the high refractive index transparent resin layer itself do not form a pattern is preferably a developer having a development behavior that does not dissolve the non-alkaline development type colored composition layer.
  • a small amount of an organic solvent miscible with water may be added to the developer.
  • organic solvents miscible with water examples include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol And acetone, methyl ethyl ketone, cyclohexanone, ⁇ -caprolactone, ⁇ -butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ⁇ -caprolactam, N-methylpyrrolidone, and the like.
  • the concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
  • a known surfactant can be further added to the developer.
  • the concentration of the surfactant is preferably 0.01% by mass to 10% by mass.
  • the development method described above may be any of paddle development, shower development, shower & spin development, dip development, and the like.
  • shower development By spraying a developer onto the transparent resin layer and the high refractive index transparent resin layer after exposure, the uncured portion can be removed.
  • an alkaline solution having a low solubility of the photocurable resin layer is sprayed by a shower or the like before development to remove the thermoplastic resin layer or the intermediate layer. It is preferable to keep it. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
  • the liquid temperature of the developer is preferably 20 ° C. to 40 ° C.
  • the pH of the developer is preferably 8 to 13.
  • the above-described laminate manufacturing method may have other steps such as a post-exposure step.
  • the patterning exposure and the entire surface exposure may be performed after the substrate (temporary support) is peeled off, or may be exposed before the temporary support is peeled, and then the temporary support may be peeled off. Exposure through a mask or digital exposure using a laser or the like may be used.
  • the method for producing a laminate of the present invention includes a step of heat-treating the transparent resin layer after transfer to make at least a part of the carboxyl group-containing acrylic resin a carboxylic acid anhydride. From the viewpoint of improving
  • the heat treatment for the transparent resin layer after transfer is preferably after exposure and development, that is, a post-baking step after exposure and development.
  • a post-baking step after exposure and development.
  • the above-mentioned transparent resin layer and the above-described high refractive index transparent resin layer are thermosetting, it is particularly preferable to perform a post-bake process.
  • a post-baking process also from a viewpoint of adjusting the resistance value of transparent electrodes, such as ITO.
  • the heating temperature in the step of heat-treating the transparent resin layer after transfer so that at least a part of the carboxyl group-containing acrylic resin is carboxylic anhydride is 100 to 160 ° C.
  • the temperature is preferably 140 to 150 ° C.
  • the laminate of the present invention has a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm on the side of the transparent electrode pattern opposite to the side on which the high refractive index transparent resin layer is formed.
  • the above-mentioned transparent film is formed into a film directly on the above-mentioned transparent electrode pattern, or through other layers, such as the above-mentioned 3rd transparent film.
  • the method for forming the transparent film is not particularly limited, but is preferably formed by transfer or sputtering.
  • the laminate of the present invention is preferably formed by transferring the transparent curable resin film formed on the temporary support onto the above-mentioned substrate, and curing after transfer.
  • the film is formed.
  • the above-mentioned transparent resin layer and the above-described high-refractive-index transparent resin layer in the laminate manufacturing method are transferred using a photosensitive film in the description of the capacitance-type input device of the present invention described later.
  • the method of performing a transfer, exposure, development, and other processes similarly to the method of performing can be mentioned. In that case, it is preferable to adjust the refractive index of the transparent film in the above range by dispersing the metal oxide particles in the photocurable resin layer in the photosensitive film.
  • the transparent film is an inorganic film, it is preferably formed by sputtering. That is, in the laminated body of the present invention, it is also preferable that the transparent film is formed by sputtering.
  • the sputtering method the methods used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.
  • the third transparent film forming method is the same as the method of forming a transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm on the substrate.
  • the method for producing a laminate preferably includes a step of simultaneously curing the transparent resin layer and the high refractive index transparent resin layer, and more preferably includes a step of pattern curing at the same time.
  • the transfer film of the present invention is preferably laminated with a high refractive index transparent resin layer without curing the transparent resin layer after laminating the transparent resin layer.
  • the transparent resin layer and the high refractive index transparent resin layer transferred from the transfer film of the present invention thus obtained can be simultaneously cured. Thereby, after transferring the transparent resin layer and the high refractive index transparent resin layer from the transfer film of the present invention onto the transparent electrode pattern, it can be developed into a desired pattern by photolithography.
  • the method for producing a laminate includes the step of simultaneously curing the transparent resin layer and the high refractive index transparent resin layer, and then the uncured portion of the transparent resin layer and the high refractive index transparent resin layer (in the case of photocuring, only the unexposed portion). It is more preferable to include a step of developing and removing only the exposed portion).
  • the 1st aspect of the capacitance-type input device of this invention is produced using the transfer film of this invention.
  • the 2nd aspect of the capacitive input device of this invention contains the laminated body of this invention.
  • the capacitance-type input device of the present invention includes a high-refractive-index transparent resin layer and a transparent resin layer disposed adjacent to the above-described high-refractive-index transparent resin layer from the transfer film of the present invention. It is preferable to transfer and produce on the electrode pattern of an apparatus. In the capacitance type input device of the present invention, it is preferable that the transparent resin layer and the high refractive index transparent resin layer transferred from the transfer film of the present invention are cured at the same time.
  • pattern curing is performed simultaneously.
  • the capacitive input device of the present invention develops and removes the uncured portions of the transparent resin layer and the high refractive index transparent resin layer that are transferred from the transfer film of the present invention and simultaneously pattern-cured.
  • FIG. 13 shows a capacitance-type input device having the following configuration including a lead wire (another conductive element 6) of a transparent electrode pattern and a terminal portion 31 of the lead wire. Since the transparent resin layer on the terminal portion 31 of the routing wiring is an uncured portion (unexposed portion), it is removed by development and the terminal portion 31 of the routing wiring is exposed. Specific exposure and development modes are shown in FIGS. FIG.
  • FIG. 14 shows a state before the transfer film 30 of the present invention having a transparent resin layer and a high refractive index transparent resin layer is laminated on a transparent electrode pattern of a capacitive input device and cured by exposure or the like. Indicates.
  • photolithography that is, when cured by exposure, the unexposed transparent resin layer and the high refractive index transparent resin layer are patterned by pattern exposure and development of the unexposed area using a mask.
  • a transparent resin layer and a high refractive index transparent resin layer 33 can be obtained. Specifically, in FIG.
  • openings 34 at the pattern ends of the transparent resin layer and the high refractive index transparent resin layer corresponding to the terminal portions of the routing wiring as uncured portions of the transparent resin layer and the high refractive index transparent resin layer.
  • the enclosed region) and the end of the transfer film of the present invention having the transparent resin layer and the high refractive index transparent resin layer that protruded outside the outline of the frame portion of the capacitive input device were removed, A patterned transparent resin layer and a high-refractive-index transparent resin layer 33 (desired pattern) for not covering the terminal portion (lead-out wiring portion) of the routing wiring are obtained.
  • the capacitance-type input device of the present invention has the laminate of the present invention, and includes at least the following (3) on the substrate (corresponding to the aforementioned substrate in the laminate of the present invention) and the non-contact surface side of the aforementioned substrate. It is preferable to have elements (8) to (8). (3) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in the first direction via the connection portions; (4) A plurality of second electrode patterns comprising a plurality of pad portions that are electrically insulated from the first transparent electrode pattern and extend in a direction intersecting the first direction.
  • the above (7) high refractive index transparent resin layer corresponds to the above high refractive index transparent resin layer in the laminate of the present invention.
  • the above-mentioned (8) transparent resin layer corresponds to the above-mentioned transparent resin layer in the laminate of the present invention.
  • the above-mentioned transparent resin layer is preferably a so-called transparent protective layer in a generally known electrostatic capacitance type input device.
  • the above-mentioned (4) second electrode pattern may or may not be a transparent electrode pattern, but is preferably a transparent electrode pattern.
  • the capacitance-type input device of the present invention further includes (2) a transparent film, (3) the first transparent electrode pattern and the substrate, and (4) the second electrode pattern and the above-described substrate. It is preferable to have between the substrates or between the aforementioned (6) another conductive element and the aforementioned substrate.
  • the above-mentioned (2) transparent film corresponds to a transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm in the laminate of the present invention. From the viewpoint of further improving the properties.
  • the capacitance-type input device of the present invention preferably further has (1) a mask layer and / or a decoration layer as necessary.
  • the mask layer described above is provided as a black frame around the area touched by a finger or a touch pen so that the transparent electrode pattern routing wiring cannot be visually recognized from the contact side or is decorated.
  • the above-mentioned decoration layer is provided for decoration as a frame around the area touched with a finger or a touch pen. For example, it is preferable to provide a white decoration layer.
  • the above-mentioned (1) mask layer and / or decorative layer is formed between the above-mentioned (2) transparent film and the above-mentioned substrate, (3) between the above-mentioned first transparent electrode pattern and the above-mentioned substrate, 4) It is preferable to have between the 2nd transparent electrode pattern and the above-mentioned board
  • the aforementioned (1) mask layer and / or decorative layer is more preferably provided adjacent to the aforementioned substrate.
  • the capacitance-type input device of the present invention includes the above-described high-refractive index transparent resin layer and the above-described high-refractive index transparent resin layer that are disposed adjacent to the transparent electrode pattern, even when various members are included.
  • the transparent electrode pattern can be made inconspicuous, and the concealment problem of the transparent electrode pattern can be improved.
  • the transparent electrode pattern is sandwiched between the transparent film having the refractive index of 1.6 to 1.78 and the thickness of 55 to 110 nm and the high refractive index transparent resin layer. As a result, the problem of concealment of the transparent electrode pattern can be improved.
  • FIG. 16 is a schematic cross-sectional view showing another example of a preferable configuration of the capacitance-type input device of the present invention.
  • 16 is a schematic cross-sectional view showing another example of the configuration of the capacitance-type input device of the present invention.
  • the terminal portion 31 of the routing wiring (another conductive element) in FIG. 14 and the routing wiring in FIG. It is an enlarged view of the vicinity of the opening part 34 corresponding to this terminal part. In the center of FIG. 16, there is an opening 34 corresponding to the terminal portion of the routing wiring.
  • FIG. 1A is a schematic cross-sectional view showing an example of a preferred configuration of the capacitive input device of the present invention.
  • a capacitive input device 10 includes a substrate 1, a mask layer 2, a transparent film 11 having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm, and a first transparent electrode pattern. (The connection portion 3b of the first transparent electrode pattern is shown), the second transparent electrode pattern 4, the insulating layer 5, another conductive element 6, and the high refractive index transparent resin layer 12 The aspect comprised from the transparent resin layer 7 is shown.
  • FIG. 1B showing an XY cross section in FIG. 3 to be described later is also a cross-sectional view showing a preferable configuration of the capacitive input device of the present invention.
  • a capacitive input device 10 includes a substrate 1, a transparent film 11 having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm, a first transparent electrode pattern 3, a second The aspect comprised from this transparent electrode pattern 4, the high refractive index transparent resin layer 12, and the transparent resin layer 7 is shown.
  • the substrate 1 can use the materials mentioned as the material of the laminate of the present invention. Moreover, in FIG. 1A, the side in which each element of the board
  • a mask layer 2 is provided on the non-contact surface of the substrate 1.
  • the mask layer 2 is a frame-shaped pattern around the display area formed on the non-contact surface side of the touch panel substrate, and is formed so as to prevent the lead-out wiring and the like from being seen.
  • a mask layer 2 is provided so as to cover a part of the substrate 1 (a region other than the input surface in FIG. 2).
  • the substrate 1 can be provided with an opening 8 in a part thereof as shown in FIG.
  • a pressing mechanical switch can be installed in the opening 8.
  • a plurality of first transparent electrode patterns 3 formed by extending a plurality of pad portions in the first direction via connection portions, a first transparent electrode pattern 3,
  • a plurality of second transparent electrode patterns 4 made of a plurality of pad portions that are electrically insulated and extend in a direction intersecting the first direction, the first transparent electrode pattern 3 and the second An insulating layer 5 that electrically insulates the transparent electrode pattern 4 is formed.
  • the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 described later those mentioned as the material for the transparent electrode pattern in the laminate of the present invention may be used.
  • An ITO film is preferable.
  • FIG. 1A a diagram is shown in which the second transparent electrode pattern 4 is installed across both regions of the non-contact surface of the substrate 1 and the surface of the mask layer 2 opposite to the substrate 1. .
  • a vacuum laminator or the like can be obtained by using a photosensitive film having a specific layer configuration to be described later. Even without using expensive equipment, it is possible to perform lamination without generating bubbles at the boundary of the mask portion with a simple process.
  • FIG. 3 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern in the present invention.
  • the first transparent electrode pattern 3 is formed such that the pad portion 3a extends in the first direction C via the connection portion 3b.
  • the second transparent electrode pattern 4 is electrically insulated from the first transparent electrode pattern 3 by the insulating layer 5, and is in a direction intersecting the first direction C (second direction D in FIG. 3). ) To be formed by a plurality of pad portions.
  • the pad portion 3a and the connection portion 3b described above may be manufactured as one body, or only the connection portion 3b is manufactured, and the pad portion 3a and the second portion 3b are formed.
  • the transparent electrode pattern 4 may be integrally formed (patterned).
  • the pad portion 3a and the second transparent electrode pattern 4 are produced (patterned) as a single body (patterning), as shown in FIG. 3, a part of the connection portion 3b and a part of the pad portion 3a are coupled, and an insulating layer Each layer is formed so that the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are electrically insulated by 5.
  • region in which the 1st transparent electrode pattern 3 in FIG. 3, the 2nd transparent electrode pattern 4, and another electroconductive element 6 mentioned later is not formed is equivalent to the non-pattern area
  • another conductive element 6 is provided on the side of the mask layer 2 opposite to the substrate 1. Another conductive element 6 is electrically connected to at least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4, and the first transparent electrode pattern 3 and the second transparent electrode pattern 4. Is a different element. In FIG. 1A, an embodiment in which another conductive element 6 is connected to the second transparent electrode pattern 4 is shown.
  • a transparent resin layer 7 is provided so as to cover all the components.
  • the transparent resin layer 7 may be configured to cover only a part of each component.
  • the insulating layer 5 and the transparent resin layer 7 may be the same material or different materials.
  • FIG. 4 is a top view showing an example of a transparent substrate 1 made of tempered glass with openings 8 formed therein.
  • FIG. 5 is a top view showing an example of the substrate on which the mask layer 2 is formed.
  • FIG. 6 is a top view showing an example of the substrate on which the first transparent electrode pattern 3 is formed.
  • FIG. 7 is a top view showing an example of a substrate on which the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are formed.
  • FIG. 8 is a top view showing an example of a substrate on which a conductive element 6 different from the first and second transparent electrode patterns is formed.
  • each element is arbitrarily formed using the transfer film of the present invention. It can be formed by transferring the above-described high refractive index transparent resin layer and the above transparent resin layer to the surface of the substrate 1.
  • the photosensitive film which has a temporary base material and a photocurable resin layer in this order.
  • the touch panel reduced in thickness and weight can be manufactured by a simple process without contaminating the non-contact surface of the substrate.
  • the photosensitive film as a permanent material such as a first transparent electrode pattern, a second transparent electrode pattern and another conductive element when a mask layer, an insulating layer, and a conductive photocurable resin layer are used
  • the photosensitive film may be subjected to pattern exposure as necessary after being laminated on the substrate.
  • the aforementioned photosensitive film may be a negative type material or a positive type material.
  • a pattern can be obtained by developing and removing the non-exposed portion and when the positive film is a positive type material.
  • thermoplastic resin layer and the photocurable resin layer may be developed and removed with separate liquids, or may be removed with the same liquid. You may combine well-known image development facilities, such as a brush and a high pressure jet, as needed. After the development, post-exposure and post-bake may be performed as necessary.
  • the above-described photosensitive film other than the transfer film of the present invention which is preferably used when manufacturing the capacitive input device of the present invention, will be described.
  • the aforementioned photosensitive film preferably has a temporary base material and a photocurable resin layer, and preferably has a thermoplastic resin layer between the temporary base material and the photocurable resin layer.
  • a mask layer or the like is formed using the photosensitive film having the thermoplastic resin layer described above, bubbles are less likely to be generated in the element formed by transferring the photocurable resin layer, and image unevenness or the like is caused in the image display device. It is less likely to occur and excellent display characteristics can be obtained.
  • production method- As the above-mentioned temporary base material and the above-mentioned thermoplastic resin layer in the above-mentioned photosensitive film, those similar to those respectively used as the temporary support and the thermoplastic resin layer in the transfer film of the present invention can be used. Moreover, the same method as the manufacturing method of a transfer film can be used also as the preparation methods of the above-mentioned photosensitive film.
  • the above-mentioned photosensitive film adds an additive to a photocurable resin layer according to the use. That is, when the above-mentioned photosensitive film is used for forming the mask layer, a colorant is contained in the photocurable resin layer. Moreover, when the above-mentioned photosensitive film has an electroconductive photocurable resin layer, electroconductive fiber etc. contain in the above-mentioned photocurable resin layer.
  • the photocurable resin layer preferably contains an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. Furthermore, conductive fibers, colorants, other additives, and the like are used, but are not limited thereto.
  • the alkali-soluble resin, the polymerizable compound, and the polymerization initiator contained in the photosensitive film the same alkali-soluble resin, polymerizable compound, or polymerization initiator as those used in the transfer film of the present invention is used. be able to.
  • the fiber having a solid structure may be referred to as “wire”, and the fiber having a hollow structure may be referred to as “tube”.
  • a conductive fiber having an average minor axis length of 1 nm to 1,000 nm and an average major axis length of 1 ⁇ m to 100 ⁇ m may be referred to as “nanowire”.
  • a conductive fiber having an average minor axis length of 1 nm to 1,000 nm, an average major axis length of 0.1 ⁇ m to 1,000 ⁇ m, and having a hollow structure may be referred to as “nanotube”.
  • the material for the conductive fiber is not particularly limited as long as it has conductivity, and can be appropriately selected according to the purpose. At least one of metal and carbon is preferable.
  • the conductive fibers are particularly preferably at least one of metal nanowires, metal nanotubes, and carbon nanotubes.
  • the above-mentioned metal nanowire consists of the 4th period, the 5th period, and the 6th period of the long period table (The International Union of Pure and Applied Chemistry (IUPAC) 1991).
  • At least one metal selected from the group is preferable, at least one metal selected from Group 2 to Group 14 is more preferable, and Group 2, Group 8, Group 9, Group 10 and Group 11 are more preferable.
  • At least one metal selected from Group 12, Group 13, and Group 14 is more preferable, and it is particularly preferable to include as a main component.
  • Examples of the metal include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, antimony, Examples thereof include lead and alloys thereof. Among these, in view of excellent conductivity, those mainly containing silver or those containing an alloy of silver and a metal other than silver are preferable. Containing mainly the above-mentioned silver means containing 50 mass% or more, preferably 90 mass% or more of silver in the metal nanowire. Examples of the metal used in the aforementioned alloy with silver include platinum, osmium, palladium and iridium. These may be used alone or in combination of two or more.
  • a shape of the above-mentioned metal nanowire there is no restriction
  • the cross-sectional shape of the above-mentioned metal nanowire can be examined by applying a metal nanowire aqueous dispersion on a temporary base material and observing the cross-section with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the average minor axis length of the metal nanowire is preferably 150 nm or less, more preferably 1 nm to 40 nm, still more preferably 10 nm to 40 nm, and particularly preferably 15 nm to 35 nm.
  • the average minor axis length is less than 1 nm, the oxidation resistance may be deteriorated and the durability may be deteriorated.
  • the average minor axis length is more than 150 nm, scattering due to metal nanowires occurs and sufficient transparency is obtained. There are things you can't get.
  • the average minor axis length of the above-mentioned metal nanowires was determined by observing 300 metal nanowires using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). The average minor axis length of the wire was determined. The short axis length when the short axis of the metal nanowire was not circular was the shortest axis.
  • the average major axis length of the metal nanowire is preferably 1 ⁇ m to 40 ⁇ m, more preferably 3 ⁇ m to 35 ⁇ m, and even more preferably 5 ⁇ m to 30 ⁇ m.
  • the average major axis length of the above-mentioned metal nanowires is determined by observing 300 metal nanowires using, for example, a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). The average major axis length of the nanowire was determined.
  • TEM transmission electron microscope
  • the thickness of the conductive photocurable resin layer is preferably from 0.1 to 20 ⁇ m, more preferably from 0.5 to 18 ⁇ m, from the viewpoint of process stability such as the stability of the coating solution and the drying time during coating and the development time during patterning. 1 to 15 ⁇ m is preferable.
  • the content of the conductive fiber with respect to the total solid content of the conductive photocurable resin layer is preferably 0.01 to 50% by mass from the viewpoint of conductivity and stability of the coating solution, and is preferably 0.05 to 30% by mass is more preferable, and 0.1 to 20% by mass is particularly preferable.
  • a coloring agent can be used for a photocurable resin layer.
  • known colorants organic pigments, inorganic pigments, dyes, etc.
  • a mixture of pigments such as red, blue, and green can be used.
  • the above-mentioned photocurable resin layer is used as a black mask layer, it is preferable to include a black colorant from the viewpoint of optical density.
  • the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, and graphite. Among these, carbon black is preferable.
  • the white pigment described in paragraphs 0015 and 0114 of JP-A-2005-7765 can be used.
  • pigments or dyes described in paragraphs 0183 to 0185 of Japanese Patent No. 4546276 may be mixed and used.
  • pigments and dyes described in paragraphs 0038 to 0054 of JP-A-2005-17716, pigments described in paragraphs 0068 to 0072 of JP-A-2004-361447, paragraphs of JP-A-2005-17521 The colorants described in 0080 to 0088 can be preferably used.
  • the aforementioned colorant (preferably a pigment, more preferably carbon black) is desirably used as a dispersion.
  • This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the aforementioned colorant and pigment dispersant in an organic solvent (or vehicle).
  • the aforementioned vehicle refers to a portion of the medium in which the pigment is dispersed when the paint is in a liquid state, and is a liquid component that binds with the aforementioned pigment to form a coating film (binder) and dissolves this. Component to dilute (organic solvent).
  • the disperser used for dispersing the pigment is not particularly limited.
  • kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, First Edition, Asakura Shoten, 2000, Item 438.
  • Known dispersers such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, a sand mill, and a bead mill.
  • fine grinding may be performed using frictional force by mechanical grinding described in page 310 of this document.
  • the aforementioned colorant is preferably a colorant having a number average particle size of 0.001 ⁇ m to 0.1 ⁇ m, more preferably 0.01 ⁇ m to 0.08 ⁇ m, from the viewpoint of dispersion stability.
  • the “particle size” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle size” is the above-mentioned particle size for a large number of particles, Among these, the average value of 100 particle diameters arbitrarily selected is said.
  • the thickness of the photocurable resin layer containing the colorant is preferably from 0.5 to 10 ⁇ m, more preferably from 0.8 to 5 ⁇ m, and particularly preferably from 1 to 3 ⁇ m, from the viewpoint of the thickness difference from the other layers.
  • content rate of the coloring agent in solid content of the coloring photosensitive resin composition for forming the photocurable resin layer containing a coloring agent From a viewpoint of fully shortening development time, 15 It is preferably ⁇ 70% by mass, more preferably 20 to 60% by mass, and still more preferably 25 to 50% by mass.
  • the total solid content of the colored photosensitive resin composition means the total mass of nonvolatile components excluding the solvent and the like from the colored photosensitive resin composition.
  • the thickness of the photocurable resin layer is preferably from 0.1 to 5 ⁇ m, more preferably from 0.3 to 3 ⁇ m from the viewpoint of maintaining insulation. 0.5 to 2 ⁇ m is particularly preferable.
  • additives may be used for the above-mentioned photocurable resin layer.
  • the same additives as those used for the transfer film of the present invention can be used.
  • the solvent similar to what is used for the transfer film of this invention can be used.
  • the above-described photosensitive film is a negative type material
  • the above-described photosensitive film may be a positive type material.
  • a positive type material for example, a material described in JP-A-2005-221726 is used for the photocurable resin layer, but is not limited thereto.
  • the mask layer 2 and the insulating layer 5 described above can be formed by transferring the photocurable resin layer to the substrate 1 or the like using the above-described photosensitive film.
  • the above-described black light is applied to the surface of the substrate 1 using the above-described photosensitive film having the black photo-curable resin layer as the above-described photo-curable resin layer. It can be formed by transferring a curable resin layer.
  • the above-mentioned substrate on which the first transparent electrode pattern is formed using the above-mentioned photosensitive film having an insulating photo-curable resin layer as the above-mentioned photo-curable resin layer. It can be formed by transferring the above-mentioned photocurable resin layer to the first transparent electrode pattern formed on the surface of 1. Furthermore, in forming the mask layer 2 that needs light shielding properties, the above photosensitive film having a specific layer structure having a thermoplastic resin layer between the photocurable resin layer and the temporary base material is used for photosensitivity. It is possible to prevent the generation of bubbles during film lamination and to form a high quality mask layer 2 or the like having no light leakage.
  • the first transparent electrode pattern 3, the second transparent electrode pattern 4, and the other conductive element 6 are etched using the above-described photosensitive film having an etching process or a conductive photo-curable resin layer, or photosensitive.
  • a film can be formed using the lift-off material.
  • the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 are formed by etching, first, on the non-contact surface of the substrate 1 on which the mask layer 2 and the like are formed.
  • a transparent electrode layer such as ITO is formed by sputtering.
  • an etching pattern is formed by exposure and development using the above-described photosensitive film having the photocurable resin layer for etching as the above-mentioned photocurable resin layer on the above-described transparent electrode layer.
  • the transparent electrode layer is etched to pattern the transparent electrode, and the etching pattern is removed, whereby the first transparent electrode pattern 3 and the like can be formed.
  • etching pattern Even when the above-described photosensitive film is used as an etching resist (etching pattern), a resist pattern can be obtained in the same manner as described above.
  • etching and resist stripping can be applied by a known method described in paragraphs 0048 to 0054 of JP 2010-152155 A.
  • an etching method there is a commonly performed wet etching method of dipping in an etching solution.
  • an etchant used for wet etching an acid type or alkaline type etchant may be appropriately selected in accordance with an object to be etched.
  • acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and mixed aqueous solutions of acidic components and salts of ferric chloride, ammonium fluoride, potassium permanganate, and the like. Is done.
  • the acidic component a combination of a plurality of acidic components may be used.
  • alkaline type etching solutions include aqueous solutions containing only alkaline components such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, salts of organic amines such as tetramethylammonium hydroxide, alkaline components and potassium permanganate, etc.
  • alkaline components such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, salts of organic amines such as tetramethylammonium hydroxide, alkaline components and potassium permanganate, etc.
  • a mixed aqueous solution of a salt of A combination of a plurality of alkali components may be used as the alkali component.
  • the temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower.
  • the resin pattern used as an etching mask (etching pattern) in the present invention is particularly excellent with respect to acidic and alkaline etching solutions in this temperature range by being formed using the photocurable resin layer described above. Demonstrate resistance. Therefore, the resin pattern is prevented from peeling off during the etching process, and the portion where the resin pattern does not exist is selectively etched.
  • a cleaning process and a drying process may be performed as necessary to prevent line contamination.
  • the cleaning process is performed by cleaning the resin pattern with pure water for 10 to 300 seconds at room temperature.
  • the air blow pressure (about 0.1 to 5 kg / cm 2 ) is appropriately adjusted using an air blow. Just do it.
  • the method of peeling the resin pattern is not particularly limited, and examples thereof include a method of immersing the resin pattern in a peeling solution being stirred at 30 to 80 ° C., preferably 50 to 80 ° C. for 5 to 30 minutes.
  • the resin pattern used as an etching mask in the present invention exhibits excellent chemical resistance at 45 ° C. or lower as described above, but exhibits a property of swelling by an alkaline stripping solution when the chemical temperature is 50 ° C. or higher. . Due to this property, when the peeling process is performed using a stripping solution of 50 to 80 ° C., there is an advantage that the process time is shortened and the peeling residue of the resin pattern decreases.
  • the resin pattern used as an etching mask in the present invention exhibits good chemical resistance in the etching step, while the peeling step. In this case, good releasability is exhibited, and both contradictory properties of chemical resistance and releasability can be satisfied.
  • the stripping solution examples include inorganic alkali components such as sodium hydroxide and potassium hydroxide, organic alkali components such as tertiary amine and quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or these.
  • a stripping solution dissolved in a mixed solution of You may peel by the spray method, the shower method, the paddle method etc. using the above-mentioned peeling liquid.
  • the substrate described above is used. It can be formed by transferring the conductive photocurable resin layer described above to the surface of 1.
  • the resist component may be leaked and / or protruded from the opening even on the substrate having the opening. Without touching the non-contact surface side of the substrate, it is possible to manufacture a touch panel having a merit of thin layer / light weight by a simple process.
  • the photosensitive film having a specific layer structure having a thermoplastic resin layer between the conductive photocurable resin layer and the temporary base material for forming the first transparent electrode pattern 3 and the like. It is possible to prevent the generation of bubbles when laminating the photosensitive film, and to form the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 with excellent conductivity and low resistance.
  • a 1st transparent electrode layer, a 2nd transparent electrode layer, and another electroconductive member can also be formed using the above-mentioned photosensitive film as a lift-off material.
  • a transparent conductive layer is formed on the entire surface of the temporary substrate, and then the above-described photoconductive resin layer is dissolved and removed together with the laminated transparent conductive layer.
  • a transparent conductive layer pattern can be obtained (lift-off method).
  • the image display device of the present invention is an image display device including the capacitive input device of the present invention as a constituent element.
  • the image display device of the present invention includes “latest touch panel technology” (published July 6, 2009, Techno Times), supervised by Yuji Mitani, “Technology and Development of Touch Panel”, CM Publishing (2004, 12), The configurations disclosed in the FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. can be applied.
  • materials B-1 to B-7 which are coating solutions for the high refractive index transparent resin layer, were prepared so as to have the compositions shown in Table 2 below.
  • Mw is synonymous with “weight average molecular weight”.
  • the coating amount is adjusted so that the thickness of the transparent resin layer after drying is as shown in Table 4 below.
  • Any one of Materials A-1 to A-16 was applied according to the following Table 4 to form a transparent resin layer.
  • the thickness of the high refractive index transparent resin layer after drying is shown in Table 5 below.
  • the amount of coating is adjusted so as to be thick, and any one of the materials B-1 to B-7 for the high refractive index transparent resin layer is applied according to the following Table 5, dried, and then the high refractive index transparent resin layer Formed.
  • a protective film (16 ⁇ m thick PET film) was pressure-bonded on the formed high refractive index transparent resin layer.
  • a temporary support, a transparent resin layer, a high refractive index transparent resin layer, and a protective film were laminated in this order to produce a transfer film.
  • the obtained transfer film was used as a transfer film of each example and comparative example.
  • the amount of the crosslinkable group in the transparent resin layer was calculated from the material composition. The obtained results are shown in Table 4 below.
  • the amount of the crosslinkable group obtained by the calculation was prepared separately by preparing a sample consisting only of the transparent resin layer, dissolving a predetermined amount of the sample in a suitable solvent, and analyzing various crosslinkable groups by analysis such as NMR or FT-IR. It was comparable to the value calculated by quantifying.
  • the I / O value of the transparent resin layer was calculated from the material composition according to the method shown in “Organic Conceptual Diagram” (Yoshio Koda, Sankyo Publishing, 1984). The obtained results are shown in Table 4 below.
  • the thickness and refractive index of the transparent resin layer and the high refractive index transparent resin layer were determined as follows using a reflection spectral film thickness meter FE-3000 (manufactured by Otsuka Electronics Co., Ltd.).
  • a transparent adhesive tape (on a temporary support surface of a sample in which only a transparent resin layer is formed on a temporary support in the same manner as in each of the Examples and Comparative Examples, which is cut to a length of 5 cm ⁇ 5 cm in length and width.
  • OCA tape 8171CL: manufactured by 3M Co., Ltd. was used to produce a laminate in which a black PET material was brought into contact.
  • TEM transmission electron microscope
  • the transparent resin layer, the temporary support, and the black PET laminate were structurally analyzed.
  • the thickness of the transparent resin layer was measured at 10 points to determine an average value, and a first expected value T 1 (I) of the average value of the thickness of the transparent resin layer was determined.
  • the reflection spectrum (wavelength: 430 to 800 nm) of the laminate of the transparent resin layer, the temporary support and the black PET was evaluated using a reflection spectral film thickness meter FE-3000 manufactured by Otsuka Electronics Co., Ltd., and the transparent resin layer at each wavelength.
  • the second expected value T 1 (II) of the average value of the refractive index n 1 and the thickness of the transparent resin layer was determined.
  • the first value of the refractive index n 0 of the temporary support obtained in (1) above and the average value of the thickness of the transparent resin layer is used.
  • the expected value T 1 (I) is input to the thickness calculation software attached to the FE 3000, and then the refractive index n 1 of the transparent resin layer and the transparent resin layer are determined from the reflection spectrum of the laminate of the transparent resin layer, the temporary support, and the black PET.
  • the second expected value T 1 (II) of the average value of the thickness was obtained by fitting by simulation calculation.
  • a transparent adhesive tape (OCA tape 8171CL: 3M Co., Ltd.) was applied to the surface of the temporary support of the transfer film of each Example and Comparative Example, which was cut into a length of 5 cm ⁇ 5 cm and the protective film was peeled off.
  • a sample piece in which a black PET material was brought into contact was prepared. Analyzing the structure of the sample piece using a transmission electron microscope (TEM), measuring the thickness of the high refractive index transparent resin layer at 10 points, obtaining the average value, and predicting the average value of the thickness of the high refractive index transparent resin layer The value T 2 (I) was determined.
  • TEM transmission electron microscope
  • 200 measurement points that is, 4 cm length
  • diameter of 40 ⁇ m at intervals of 0.2 mm using a reflection spectral film thickness meter FE-3000.
  • FE-3000 Reflection spectrum of 200 measurement points (that is, 4 cm length) on a straight line in an arbitrary direction at a measurement spot: diameter of 40 ⁇ m at intervals of 0.2 mm using a reflection spectral film thickness meter FE-3000.
  • the refractive index n 0 of the temporary support obtained in (1) above
  • the second expected value T 1 (II) of the average value of the refractive index n 1 of the transparent resin layer and the thickness of the transparent resin layer obtained in (2), and the expected value of the average value of the thickness of the high refractive index transparent resin layer With the value T 2 (I) substituted into the calculation formula, the refractive index n 2 of the high refractive index transparent resin layer is determined from the reflection spectrum of the laminate of the high refractive index transparent resin layer, the transparent resin layer, the temporary support, and the black PET.
  • the thicknesses of the transparent resin layer and the high refractive index transparent resin layer at 1000 measurement points were obtained by fitting by simulation calculation. Furthermore, the average value of the thickness of a transparent resin layer and a high refractive index transparent resin layer was computed, and it was set as the thickness of the transparent resin layer and the thickness of a high refractive index transparent resin layer. As for the thickness of the transparent resin layer and the thickness of the high-refractive-index transparent resin layer, it is possible to improve the fitting accuracy of the simulation by inputting the expected value obtained by conducting the structural analysis with TEM to the reflection spectral film thickness meter. The thickness of the obtained transparent resin layer, the thickness of the high refractive index transparent resin layer, and the refractive index at a wavelength of 550 nm are shown in Table 4 or Table 5 below.
  • the material of material-C shown in Table 3 below was coated on a transparent film substrate using a slit-shaped nozzle, and then irradiated with ultraviolet rays (accumulated light amount 300 mJ / cm 2 ) and dried at about 110 ° C. As a result, a transparent film having a refractive index of 1.60 and a thickness of 80 nm was formed.
  • a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle.
  • an intermediate layer coating solution having the following formulation P1 was applied and dried.
  • a coating liquid for photocurable resin layer for etching having the following formulation E1 was applied and dried.
  • a protective film (12 ⁇ m thick polypropylene film) was pressure-bonded.
  • a photosensitive film E1 for etching in which the temporary base material, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the photocurable resin layer for etching were integrated was produced.
  • Photocurable resin layer coating solution for etching Formula E1-- Methyl methacrylate / styrene / methacrylic acid copolymer (copolymer composition (mass%): 31/40/29, Weight average molecular weight 60000, acid value 163 mg KOH / g): 16 parts by mass Monomer 1 (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.) : 5.6 parts by mass-tetramethylene oxide monomethacrylate 0.5 mol adduct of hexamethylene diisocyanate: 7 parts by mass-cyclohexane dimethanol monoacrylate as a compound having one polymerizable group in the molecule: 2.8 parts by mass ⁇ 0.42 parts by mass of 2-chloro-N-butylacridone ⁇ 2,2-bis (ortrochlorophenyl) -4,4 ′, 5,5 ′ -Tetraphenyl: 2.17 parts by mass Malachite
  • thermoplastic resin layer and the intermediate layer were transferred to the surface of the transparent electrode layer together with the photocurable resin layer for etching.
  • the distance between the surface of the exposure mask (quartz exposure mask having a transparent electrode pattern) and this photocurable resin layer for etching is set to 200 ⁇ m, and the photocurable property for etching is set via the thermoplastic resin layer and the intermediate layer.
  • the resin layer was subjected to pattern exposure at an exposure amount of 50 mJ / cm 2 (i-line). Next, using a triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) diluted 10 times with pure water) at 25 ° C. for 100 times.
  • thermoplastic resin layer and the intermediate layer are dissolved, and a surfactant-containing cleaning solution (trade name: T-SD3 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) is used. Washing was performed at 33 ° C. for 20 seconds. Pure water is sprayed from an ultra-high pressure washing nozzle, the residue on the thermoplastic resin layer is removed with a rotating brush, and further post-baking treatment is performed at 130 ° C. for 30 minutes, and a transparent film and a transparent electrode layer are formed on the transparent film substrate. A film in which a photocurable resin layer pattern for etching was formed was obtained.
  • a surfactant-containing cleaning solution trade name: T-SD3 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water
  • a film in which a transparent film, a transparent electrode layer, and a photocurable resin layer pattern for etching are formed on a transparent film substrate is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), Processed for 100 seconds (etching process), dissolved and removed the transparent electrode layer in the exposed region not covered with the photocurable resin layer for etching, and a film with a transparent electrode pattern with the photocurable resin layer pattern for etching Got.
  • ITO etchant hydroochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.
  • a film with a transparent electrode pattern having a photocurable resin layer pattern for etching is applied to a resist stripping solution (N-methyl-2-pyrrolidone, monoethanolamine, a surfactant (trade name: Surfynol 465, air (Products) Liquid temperature 45 ° C) is immersed in a resist stripping tank, treated for 200 seconds (peeling treatment), the photocurable resin layer for etching is removed, and a transparent film and a transparent electrode pattern are formed on the transparent film substrate.
  • the formed transparent electrode pattern film was obtained.
  • the surface of the obtained laminate is temporarily exposed to an exposure mask (quartz exposure mask having an overcoat formation pattern) surface.
  • the distance between the support and the support was set to 125 ⁇ m, and pattern exposure was performed at an exposure amount of 80 mJ / cm 2 (i-line) through the temporary support.
  • the laminate (film substrate) after pattern exposure was washed with a 1% by mass aqueous sodium carbonate solution at 33 ° C. for 55 seconds. Residues were removed by spraying ultrapure water from the ultra-high pressure cleaning nozzle onto the transparent film substrate after the cleaning treatment.
  • the obtained laminate of the first aspect was used as a laminate of each example and comparative example.
  • the cross-sectional shape of the pattern edge of the formed transparent resin layer pattern and high refractive index transparent resin layer pattern is observed using a surface scanning electron microscope, and consists of a high refractive index transparent resin layer pattern and a transparent resin layer pattern.
  • the depth of the undercut entering the pattern edge of the two layers was measured.
  • the undercut depth is a value determined depending on the type of transfer film, and is a value determined regardless of process conditions such as exposure, development, and post-baking. The obtained results are shown in Table 5 below.
  • the fluorescent lamp (light source) and the produced evaluation substrate are incident on the transparent film substrate surface side of the evaluation substrate, and the reflected light from the surface of the transparent film substrate on which the light is incident is obliquely It observed visually and evaluated the transparent electrode pattern concealment property based on the following evaluation criteria.
  • A, B or C is at a practical level, preferably A or B, and more preferably A.
  • C A transparent electrode pattern is visible (unclear).
  • D The transparent electrode pattern is clearly visible (easy to understand).
  • a laminate obtained by laminating a transparent film, a transparent electrode pattern, a high refractive index transparent resin layer pattern and a transparent resin layer pattern in this order on a transparent film substrate was performed by visual observation and observation with an optical microscope.
  • a or B is preferable, and A is more preferable.
  • evaluation criteria A: A residue cannot be confirmed visually in an unexposed part.
  • B A slight residue can be confirmed visually in the unexposed area.
  • C There is a portion that is not developed in the unexposed portion, and many residues can be visually confirmed.
  • D The temporary support could not be peeled from the substrate, and the developability could not be evaluated.
  • the transparent resin layer and the transparent resin layer were transferred to the subsequent processes (temporary support peeling, exposure, development, post-baking, etc.).
  • 5 cm 3 of salt water with a concentration of 50 g / L is dropped on the surface of the sample and uniformly spread to 50 cm 2 , and then the water is volatilized at room temperature, at high temperature and high humidity (85 ° C., relative humidity 85%). Aged for 24 hours. Then, the salt water was wiped off, the surface state of the sample was observed, and evaluated according to the following scores.
  • A, B or C is preferred, A or B is more preferred, and A is particularly preferred.
  • Evaluation criteria A: No change on copper, high refractive index transparent resin layer and transparent resin layer surface B: Some traces are visible on the high refractive index transparent resin layer and transparent resin layer surface, but copper does not change. C: Traces are visible on the surface of the high refractive index transparent resin layer and the transparent resin layer, but copper remains unchanged. D: Copper is discolored.
  • the transfer film of the present invention has a good concealability of the transparent electrode pattern when laminated on the transparent electrode pattern, and a laminate having excellent pattern end durability when the pattern is formed after transfer. It was found that can be formed. Specifically, the transfer film of the present invention having a low swelling rate is less likely to be undercut during pattern formation, and as a result, the copper surface is transformed from the pattern end to the inside of the two layers of the high refractive index transparent resin layer and the transparent resin layer. Progress could be suppressed. Further, the transfer film of the present invention is excellent in pattern concealing property because the refractive index of the high refractive index transparent resin layer is larger than the refractive index of the transparent resin layer.
  • the transfer films of Comparative Examples 1 to 3 having a large swelling rate were likely to be undercut at the time of pattern formation, resulting in poor pattern end durability.
  • the reason is considered to be that the copper surface has been modified from the pattern end of the two layers comprising the high refractive index transparent resin layer and the transparent resin layer to the inside. Deterioration of the copper surface leads to an increase in local resistance, leading to functional failure of the film sensor.
  • the transfer film of Comparative Example 4 in which the refractive index of the high refractive index transparent resin layer was equivalent to the refractive index of the transparent resin layer resulted in significantly inferior transparency of the transparent electrode pattern.
  • the content of the metal oxide particles in the high refractive index transparent resin layer of the laminate of each Example and Comparative Example was measured by the following method, it was the value described in Table 5 above.
  • the cross section is observed with a TEM (transmission electron microscope).
  • the ratio of the area occupied by the metal oxide particles in the film cross-sectional area of the high refractive index transparent resin layer is measured at any three locations in the layer, and the average value is regarded as the volume fraction (VR).
  • the volume fraction (VR) and the weight fraction (WR) are calculated by the following formula to calculate the weight fraction (WR) of the metal oxide particles in the high refractive index transparent resin layer.
  • WR D * VR / (1.1 * (1-VR) + D * VR)
  • D Specific gravity of metal oxide particles
  • content of the metal oxide particle of the high refractive index transparent resin layer of the laminated body of each Example and a comparative example can also be computed from the composition of a high refractive index transparent resin layer.
  • a front glass plate is further formed.
  • the capacitive input device and the image display device including the laminated body of each example had no problem that the transparent electrode pattern was visually recognized.
  • the transparent resin layer and the high refractive index transparent resin layer were free from defects such as bubbles, and an image display device excellent in display characteristics was obtained.

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Abstract

L'invention concerne un film de transfert qui comprend, dans l'ordre indiqué, un support temporaire, une couche de résine transparente et une couche de résine transparente à indice de réfraction élevé adjacente à la couche de résine transparente de façon à être en contact direct avec cette dernière ; l'indice de réfraction de la couche de résine transparente à indice de réfraction élevé étant supérieur à l'indice de réfraction de la couche de résine transparente, et le taux de gonflement de deux couches comprenant la couche de résine transparente et la couche de résine transparente à indice de réfraction élevé étant de 6,0% ou moins. Ledit film, lorsqu'il est stratifié sur un motif d'électrode transparent, fournit une bonne couverture du motif d'électrode transparent, et, une fois des motifs formés à la suite du transfert, peut former un stratifié ayant une excellente durabilité de motif. Le taux de gonflement des deux couches comprenant la couche de résine transparente et la couche de résine transparente à indice de réfraction élevé est une valeur qui représente, en pourcentage, le rapport de la quantité de variation de l'épaisseur du film avant et après que la couche de résine transparente et la couche de résine transparente à indice de réfraction élevé, ayant été transférées du film de transfert sur la feuille de cuivre d'un film stratifié de feuille de cuivre et exposé à une exposition de 80 mJ/cm2, sont immergées pendant 55 secondes dans une solution aqueuse à 1% en masse de carbonate de sodium à 33°C, sur l'épaisseur du film avant l'immersion. L'invention concerne également un stratifié ; un dispositif d'entrée de type capacitif ; et un dispositif d'affichage d'image.
PCT/JP2016/060303 2015-03-31 2016-03-30 Film de transfert, stratifié, dispositif d'entrée de type capacitif et dispositif d'affichage d'image Ceased WO2016159043A1 (fr)

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CN111095182A (zh) * 2017-09-29 2020-05-01 富士胶片株式会社 触摸传感器及触摸传感器的制造方法以及图像显示装置
CN112789166A (zh) * 2018-10-18 2021-05-11 富士胶片株式会社 转印膜、固化膜的制造方法、层叠体的制造方法、及触摸面板的制造方法
US11187972B2 (en) 2016-10-21 2021-11-30 Hoya Corporation Reflective mask blank, method of manufacturing reflective mask and method of manufacturing semiconductor device
TWI766902B (zh) * 2016-12-08 2022-06-11 日商富士軟片股份有限公司 轉印膜、電極保護膜、積層體、靜電電容型輸入裝置及觸控面板的製造方法
WO2025074559A1 (fr) * 2023-10-05 2025-04-10 株式会社レゾナック Élément photosensible, procédé de formation de motif de résine photosensible et procédé de fabrication de carte de circuit imprimé

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