WO2017169257A1 - 転写フィルム、静電容量型入力装置の電極保護膜、積層体および静電容量型入力装置 - Google Patents

転写フィルム、静電容量型入力装置の電極保護膜、積層体および静電容量型入力装置 Download PDF

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Publication number
WO2017169257A1
WO2017169257A1 PCT/JP2017/005833 JP2017005833W WO2017169257A1 WO 2017169257 A1 WO2017169257 A1 WO 2017169257A1 JP 2017005833 W JP2017005833 W JP 2017005833W WO 2017169257 A1 WO2017169257 A1 WO 2017169257A1
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Prior art keywords
resin layer
film
curable resin
electrode pattern
transparent electrode
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PCT/JP2017/005833
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English (en)
French (fr)
Japanese (ja)
Inventor
陽平 有年
豊岡　健太郎
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to KR1020187022694A priority Critical patent/KR102078112B1/ko
Priority to CN201780012670.7A priority patent/CN108698370B/zh
Publication of WO2017169257A1 publication Critical patent/WO2017169257A1/ja

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    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0443—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a single layer of sensing electrodes
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04111—Cross over in capacitive digitiser, i.e. details of structures for connecting electrodes of the sensing pattern where the connections cross each other, e.g. bridge structures comprising an insulating layer, or vias through substrate

Definitions

  • the present invention relates to a transfer film, an electrode protective film of a capacitive input device, a laminate, and a capacitive input device.
  • a liquid crystal display device having a touch panel type input device, and a finger or a touch pen is used for an image displayed on the liquid crystal display device.
  • Such input devices touch panels
  • Such 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.
  • electrode patterns are extended in directions intersecting with each other, and when a finger or the like comes in contact, the capacitance between the electrodes is detected to detect an input position.
  • Patent Documents 1 to 3 There are types (see, for example, Patent Documents 1 to 3).
  • Patent Document 4 discloses a transparent substrate having a refractive index of 1.6 to 1.78 so that the transparent electrode pattern of the capacitive input device described in Patent Documents 1 to 3 is not visually recognized.
  • a region in which a first transparent film having a thickness of 55 to 110 nm, a transparent electrode pattern, and a second transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm are stacked in this order is in-plane.
  • a laminate comprising is disclosed.
  • Various methods are known as a method of forming a transparent film as described in Patent Document 4.
  • Patent Document 4 describes a method of sputtering a metal oxide and a method of transferring a curable resin layer formed on a temporary support onto a substrate.
  • Patent Document 4 an opening for installing a pressure-sensitive switch (a pressure-type mechanical mechanism, not a capacitance change) is formed in a part of a front plate (a surface that is directly contacted with a finger).
  • a pressure-sensitive switch a pressure-type mechanical mechanism, not a capacitance change
  • the transfer film is used to prevent the resist component from leaking or protruding from the opening, and the production process is improved by eliminating the step of removing the leaked or protruding portion.
  • Patent Document 5 has a temporary support, a curable resin layer, and a second resin layer disposed adjacent to the curable resin layer in this order, and the refractive index of the second resin layer. Discloses a transfer film having a refractive index higher than that of the curable resin layer and a refractive index of the second resin layer of 1.6 or more.
  • Patent Document 6 discloses a method for forming a resin pattern having good developability using a photosensitive composition containing a resin having an acidic group in a side chain, a polymerizable compound, and a photopolymerization initiator. Are listed.
  • Patent Document 5 after forming a curable resin layer on a temporary support, a transfer film is formed by curing the curable resin layer by exposure and then laminating a second resin layer by coating. Yes.
  • the generally used capacitive input device is provided with a frame around the image display area. Therefore, the refractive index adjustment layer (layer for making the transparent electrode pattern difficult to see and improving the transparency of the transparent electrode pattern) and the transparent protective layer (overcoat layer) of the capacitive input device using the transfer film.
  • the refractive index adjustment layer is laminated on the image display area to solve the problem of seeing the transparent electrode pattern, and at the same time, the refractive index adjustment layer and the transparent protective layer are not laminated on the frame portion. Thus, it is required to be easily formed into a desired pattern shape.
  • a method for forming a desired pattern a method (die-cut method or half-cut method) in which the shape of the transfer film is cut according to the shape of the frame portion of the capacitive input device can be considered.
  • at least one of the refractive index adjustment layer and the transparent protective layer is transferred from the transfer film onto the transparent electrode pattern, and then developed into a desired pattern using photolithography. It is desired to form a laminate having good properties (patterning properties using photolithography).
  • the inventors of the present invention manufactured a transfer film provided with a protective film without curing the curable resin layer for the purpose of imparting photolithography properties.
  • a part of the uncured curable resin layer is transferred to the protective film, and the transfer defect of the curable resin layer (a part of the curable resin layer is lost).
  • many defects were generated. This is because a part of the curable resin layer adheres to the protective film that should not be transferred due to the high adhesiveness of the uncured curable resin layer.
  • the inventors of the present invention diligently studied to solve the transfer defects of the curable resin layer, and find out that the transfer defects of the curable resin layer can be reduced by increasing the surface roughness Ra of the protective film. It came. However, it has been found that the transfer film having the surface roughness Ra of the protective film increased has a problem that many bubbles are generated at the interface between the protective film and the curable resin layer.
  • the present invention has been made in view of the present situation.
  • the problem to be solved by the present invention is to provide a transfer film having photolithographic properties, less bubbles and less transfer defects.
  • Another problem to be solved by the present invention is an electrode protective film of a capacitive input device having a photolithographic property, generating less bubbles, and having a temporary support removed from a transfer film with few transfer defects, It is an object of the present invention to provide a laminated body having an electrode protective film of the capacitive input device, an electrode protective film of the capacitive input device, or a capacitive input device including the laminated body.
  • the inventors of the present invention have found that the above-mentioned problems can be solved by combining a protective film in which the surface roughness Ra and the oxygen transmission coefficient are controlled in a specific range with an uncured curable resin layer. It was.
  • the present invention which is a specific means for solving the above problems, and preferred embodiments of the present invention are as follows.
  • the oxygen permeability coefficient of the protective film is 100 cm 3 ⁇ 25 ⁇ m / m 2 ⁇ 24 hours ⁇ atm or more, A transfer film having a surface roughness Ra of 5 to 60 nm on the side of the curable resin layer of the protective film.
  • the transfer film according to [1] or [2], wherein the thickness of the protective film is 10 to 75 ⁇ m.
  • the curable resin layer includes a polymerizable compound and a binder polymer, The transfer film according to any one of [1] to [10], wherein the binder polymer is an alkali-soluble resin.
  • a transfer film having photolithographic properties, less bubbles, and less transfer defects.
  • an electrode protective film it is possible to provide an electrode protective film, a laminate, a capacitive input device, and an image display device of a capacitive input device.
  • FIG. 1 shows 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 curable resin layer .
  • 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 comprises a temporary support, A curable resin layer; A protective film;
  • the oxygen permeability coefficient of the protective film is 100 cm 3 ⁇ 25 ⁇ m / m 2 ⁇ 24 hours ⁇ atm or more,
  • the surface roughness Ra on the curable resin layer side of the protective film is 5 to 60 nm.
  • the oxygen permeability coefficient of the protective film By setting the oxygen permeability coefficient of the protective film to 100 cm 3 ⁇ 25 ⁇ m / m 2 ⁇ 24 hours ⁇ atm or more, air bubbles are discharged out of the transfer film through the protective film.
  • the surface roughness Ra of the curable resin layer side of the protective film by setting the surface roughness Ra of the curable resin layer side of the protective film to 60 nm or less, the amount of gas mixed when the protective film is laminated on the surface of the curable resin layer side can be reduced, and bubbles are generated. Can be reduced.
  • the surface roughness Ra of the protective film By setting the surface roughness Ra of the protective film to 5 nm or more, the adhesion between the protective film and the curable resin layer can be lowered, and transfer defects can be reduced.
  • the layer has a curing property
  • C C bond from the 810 cm -1
  • This can be detected by measuring the peak intensity.
  • a curing step at least one of exposure and heating
  • the curable resin layer is preferably a curable resin layer having a double bond consumption rate of less than 10%.
  • the curable resin layer may not be cured.
  • the double bond consumption rate of the curable resin layer is 0%.
  • the curable resin layer may be cured with a double bond consumption rate of less than 10%, in which case the double bond consumption rate of the curable resin layer exceeds 0%. Less than 10%.
  • the double bond consumption rate of the curable resin layer is more preferably 0%.
  • the property of the curable resin layer being curable only needs to be satisfied before exposure for photolithography.
  • the curable resin layer is exposed to a curable resin layer (preferably the double bond consumption rate is less than 10%), and the double bond consumption rate of the curable resin layer is 10% or more. It may be.
  • the curable resin layer (and the second resin layer, if necessary) is processed into a desired pattern by photolithography before transferring it to the transfer object, thereby increasing the double bond consumption rate. Then, the curable resin layer (and the second resin layer as necessary) may be transferred to the transfer target.
  • the transfer film of the present invention transfers the curable resin layer (and the second resin layer, if necessary) to the transfer object, and then transfers the curable resin layer (and the second resin if necessary) to a desired pattern. May be processed by photolithography to increase the double bond consumption rate to 10% or more.
  • preferred embodiments of the transfer film of the present invention will be described.
  • the transfer film of the present invention has a temporary support, a curable resin layer, and a protective film in this order.
  • the temporary support and the curable resin layer may be arranged in direct contact with each other, or may be arranged via another layer. Examples of the other layer include a second resin layer, a thermoplastic resin layer, and an intermediate layer described later.
  • the temporary support and the curable resin layer are preferably disposed in direct contact with each other.
  • FIG. 12 is a schematic view of the transfer film 30 in which the temporary support 26, the curable resin layer 7, the second resin layer 12, and the protective film 29 are laminated in direct contact with each other in this order.
  • the transfer film is preferably in direct contact with the curable resin layer and the second resin layer from the viewpoint of production simplicity.
  • the transfer film is preferably in direct contact with the second resin layer and the protective film from the viewpoint of reducing transfer defects.
  • the transfer film is preferably roll-shaped.
  • the transfer film moves to another portion of the transfer film where the dent defect due to the foreign matter overlaps, and the dent defect tends to increase.
  • dent defects due to foreign matters defects in which the curable resin layer and / or the second resin layer are recessed
  • dent defects due to foreign matters can be reduced. Therefore, even when the transfer film has a roll shape, dent defects can be reduced.
  • the transfer film of the present invention has a protective film, the oxygen permeability coefficient of the protective film is 100 cm 3 ⁇ 25 ⁇ m / m 2 ⁇ 24 hours ⁇ atm or more, and the surface roughness Ra on the curable resin layer side of the protective film is 5 to 60 nm.
  • the oxygen permeability coefficient of the protective film is 100 cm 3 ⁇ 25 ⁇ m / m 2 ⁇ 24 hours ⁇ atm or more.
  • the oxygen permeability coefficient of the protective film is preferably 5000 cm 3 ⁇ 25 ⁇ m / m 2 ⁇ 24 hours ⁇ atm or less.
  • the oxygen permeability coefficient of the protective film is more preferably 100 to 5000 cm 3 ⁇ 25 ⁇ m / m 2 ⁇ 24 hours ⁇ atm, more preferably 200 to 4500 cm 3 ⁇ 25 ⁇ m / m 2 ⁇ 24 hours ⁇ atm, and more preferably 500 to 4000 cm 3 ⁇ 25 ⁇ m.
  • the generation of bubbles can be reduced by setting the oxygen permeability coefficient of the protective film to 100 cm 3 ⁇ 25 ⁇ m / m 2 ⁇ 24 hours ⁇ atm or more. From the viewpoint of obtaining the effect of reducing the generation of bubbles, there is no limit on the upper limit value of the oxygen transmission coefficient of the protective film.
  • the oxygen permeability coefficient of the protective film By setting the oxygen permeability coefficient of the protective film to 5000 cm 3 ⁇ 25 ⁇ m / m 2 ⁇ 24 hours ⁇ atm or less, the strength of the protective film can be maintained and dent defects can be reduced.
  • the oxygen permeability coefficient of the protective film can be measured using a gas permeability measuring device (for example, GTR-31A, manufactured by GTR Tech Co., Ltd.) according to, for example, the differential pressure method described in JIS K7126-1. .
  • the oxygen permeability coefficient of the protective film is the same value as that of the protective film alone before the production even when the protective film is peeled off from the state of the transfer film.
  • the surface roughness Ra of the protective film on the side of the curable resin layer is 5 to 60 nm, preferably 10 to 50 nm, and more preferably 15 to 45 nm.
  • the surface roughness Ra means arithmetic average roughness.
  • the surface roughness Ra of the protective film is determined by measuring the unevenness of the surface of the protective film using a fine shape measuring instrument (for example, ET-350K, manufactured by Kosaka Laboratory Ltd.), and using the obtained measured values. In accordance with B 0601-2001, it can be obtained by calculation using 3D analysis software or the like.
  • the surface roughness Ra of the protective film is the same value as in the case of the protective film alone before the production even when the protective film is peeled off from the state of the transfer film.
  • the thickness of the protective film is preferably 10 to 75 ⁇ m, more preferably 20 to 65 ⁇ m, and even more preferably 25 to 35 ⁇ m.
  • a curable resin layer or a second resin layer thereon
  • a curable property preferably having a double bond consumption rate of less than 10%
  • laminating a protective film When the transferred film is rolled up, a dent defect is likely to occur in the curable resin layer (and / or the second resin layer). It is estimated that foreign matter generated in the manufacturing process is wound in a state where it adheres to the protective film, and the wrapping pressure causes a trace through the foreign matter, causing the curable resin layer (and / or the second resin layer) to collapse.
  • the curable resin layer (and / or the second resin layer preferably having a double bond consumption rate of less than 10%) that is curable (preferably having a double bond consumption rate of less than 10%) is soft. Dent defect is likely to occur. In order to suppress image distortion or the like in the image display device, it is preferable to reduce the number of dent defects.
  • the thickness of the protective film is preferably 10 ⁇ m or more from the viewpoint of reducing dent defects (defects in which the curable resin layer and / or the second resin layer are recessed).
  • the thickness of the protective film is preferably 25 to 35 ⁇ m from the viewpoint that all of bubbles, transfer defects, and dent defects can be reduced.
  • resin of a protective film there is no restriction
  • the resin for the protective film include polyester (preferably polyethylene terephthalate), polyolefin (preferably polypropylene), polyvinyl chloride, polycarbonate, and the like.
  • the protective film preferably contains polyethylene terephthalate or polypropylene, and the protective film more preferably contains polypropylene.
  • a polyester (preferably polyethylene terephthalate) film and a polyolefin (preferably polypropylene) film having a surface roughness Ra in the above preferred range have not been used as protective films for transfer films. It is preferable to use a polyester film and a polyolefin film having a surface roughness Ra in the above preferred range.
  • the method for controlling the surface roughness Ra of the polyester film and the polyolefin film include a method for controlling the degree of orientation of the protective film, a method for controlling the density, and a method for smoothing or roughening the surface.
  • a polyolefin (preferably polypropylene) film has conventionally had a large surface roughness Ra.
  • the surface roughness Ra of the polyolefin (preferably polypropylene) film is preferably reduced by controlling the stretching condition and the cooling condition after stretching to control the crystal state, and is preferably controlled within the above-mentioned preferable range.
  • the method for controlling the oxygen permeability coefficient of the protective film include a method for controlling the degree of orientation of the protective film, a method for controlling the density, and a method for smoothing or roughening the surface.
  • the protective film among the protective films described in paragraphs 0083 to 0087 and 0093 of JP-A-2006-259138, those having an oxygen transmission coefficient and a surface roughness within the above ranges can be appropriately used.
  • a commercially available protective film may be used as the protective film.
  • Examples of commercially available protective films include Alfan E201F, Alphan FG201 (manufactured by Oji F-Tex Co., Ltd., polypropylene film), NF-15 (manufactured by Tamapoli Co., Ltd.), and the like.
  • the transfer film of the present invention has a temporary support. There is no restriction
  • the thickness of the temporary support is not particularly limited and is preferably in the range of 5 to 200 ⁇ m.
  • the thickness of the temporary support is more preferably in the range of 10 to 150 ⁇ m from the viewpoint of easy handling and versatility.
  • the temporary support is preferably a film, and more preferably a resin film.
  • a film used as a temporary support a material that has flexibility and does not cause significant deformation, shrinkage, or elongation under pressure, or under pressure and heat can be used.
  • Examples of such a temporary support 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 preferable.
  • the temporary support may be transparent or may contain dyed silicon, alumina sol, chromium salt, zirconium salt or the like. Conductivity can be imparted to the temporary support by the method described in JP-A-2005-221726.
  • the transfer film of the present invention has a curable resin layer.
  • the double bond consumption rate of the curable resin layer is preferably less than 10%, and more preferably 0%.
  • the double bond consumption rate of the curable resin layer is, for example, using a Fourier transform infrared spectrophotometer (FT-IR), etc., for the curable resin layer immediately after coating and drying, and for the slice of the curable resin layer in the transfer film,
  • FT-IR Fourier transform infrared spectrophotometer
  • the peak intensities A 1 and B 1 derived from C ⁇ C bonds at a specific wavelength can be obtained and calculated by the following formula.
  • Double bond consumption rate of curable resin layer ⁇ 1- (B 1 / A 1 ) ⁇ ⁇ 100%
  • the curable resin layer may be thermosetting, photocurable, thermosetting and photocurable. It is preferable that the curable resin layer is at least thermosetting from the viewpoint that the film can be thermoset after transfer to impart film reliability. It is more preferable that the curable resin layer is thermosetting and photocurable from the viewpoint of being easy to be photocured and formed into a film after the transfer, and thermosetting after forming the film to impart the reliability of the film.
  • the cured layer obtained by curing the curable resin layer may lose curability (thermosetting or photocuring).
  • a cured layer that has lost its curability is also referred to as a curable resin layer.
  • the refractive index n 1 of the curable resin layer is preferably 1.45 ⁇ n 1 ⁇ 1.59, more preferably 1.5 ⁇ n 1 ⁇ 1.53, and 1.5 ⁇ n 1 ⁇ 1.52 is more preferable, and 1.51 ⁇ n 1 ⁇ 1.52 is particularly preferable.
  • a curable resin layer having a desired refractive index is used alone, a curable resin layer to which particles such as metal particles or metal oxide particles are added, or a composite of a metal salt and a polymer is used. Can be.
  • the thickness of the curable resin layer is preferably 1 to 20 ⁇ m, more preferably 2 to 15 ⁇ m, and even more preferably 3 to 12 ⁇ m.
  • the curable resin layer is preferably used for an image display portion of a capacitance type input device. In that case, it is important that the curable resin layer has high transparency and high transmittance. When the thickness of the curable resin layer is sufficiently thin, a decrease in transmittance due to absorption of the curable resin layer is less likely to occur, and yellowing due to absorption of short waves is less likely to occur.
  • T 1 represents the average thickness of the curable resin layer.
  • the term “thickness of the curable resin layer” refers to “average thickness T 1 of the curable resin layer” unless otherwise specified.
  • the curable resin layer is preferably alkali-soluble. That the resin layer is alkali-soluble means that the resin layer is dissolved by a weak alkaline aqueous solution.
  • the curable resin layer is more preferably developable with a weak alkaline aqueous solution.
  • the curable resin layer may be a negative material or a positive material, and is preferably a negative material.
  • the curable resin layer preferably contains a binder polymer, a polymerizable compound, a polymerization initiator, and a compound that can react with an acid by heating.
  • the curable resin layer may further include metal oxide particles.
  • the curable resin layer may further contain an additive.
  • the curable resin layer preferably contains a binder polymer.
  • the binder polymer of the curable resin layer is preferably an alkali-soluble resin.
  • alkali-soluble resin is preferably a carboxyl group-containing resin.
  • the curable resin layer preferably further contains a compound (preferably a blocked isocyanate) that can react with an acid by heating.
  • the curable resin layer contains a carboxyl group-containing resin and a compound capable of reacting with an acid by heating (preferably a blocked isocyanate)
  • the three-dimensional crosslinking density of the curable resin layer is increased by thermal crosslinking, so that the carboxyl group
  • the carboxyl group of the containing resin can be dehydrated and hydrophobized.
  • the wet heat resistance of the curable resin layer can be increased.
  • the detail of the compound which can react with an acid by heating is mentioned later.
  • the binder polymer contained in the curable resin layer preferably contains an acrylic resin.
  • a 2nd resin layer contains resin which has an acid group.
  • Interlayer adhesion between the curable resin layer and the second resin layer is that the binder polymer contained in the curable resin layer and the resin having an acid group contained in the second resin layer both contain an acrylic resin. From the viewpoint of enhancing the ratio, it is more preferable.
  • the binder polymer contained in the curable resin layer is particularly preferably a binder polymer that is a carboxyl group-containing resin and is an acrylic resin.
  • the curable resin layer may contain a binder polymer other than the carboxyl group-containing resin.
  • a binder polymer any polymer component can be used without particular limitation.
  • the other binder polymer is preferably a binder polymer having a high surface hardness and high heat resistance when the curable resin layer is used as a transparent protective layer of a capacitive input device.
  • the other binder polymer is more preferably an alkali-soluble resin. Examples of other binder polymers include known photosensitive siloxane resin materials as alkali-soluble resins.
  • the binder polymer contained in the curable resin layer is not particularly limited as long as it is not contrary to the gist of the present invention, and can be appropriately selected from known ones.
  • the polymer described in paragraph 0025 of JP2011-95716A, JP The polymers described in paragraphs 0033 to 0052 of 2010-237589 are preferably used.
  • the following compound A is mentioned as a preferable example of the binder polymer which is carboxyl group-containing resin and is an acrylic resin.
  • the acid value of the binder polymer is preferably 60 to 200 mgKOH / g, more preferably 60 to 150 mgKOH / g, and still more preferably 60 to 110 mgKOH / g.
  • the acid value of the binder polymer the theoretical acid value calculated by the calculation method described in paragraph 0063 of JP-A No. 2004-149806, paragraph 0070 of JP-A No. 2012-212228, and the like can be used.
  • the curable resin layer may contain a polymer latex as a binder polymer.
  • the polymer latex referred to here is a dispersion of water-insoluble polymer particles in water.
  • the polymer latex is described, for example, in Soichi Muroi, “Chemistry of Polymer Latex (published by Polymer Press Society (Showa 48))”.
  • Polymer particles include acrylic, vinyl acetate, rubber (for example, styrene-butadiene, chloroprene), olefin, polyester, polyurethane, polystyrene, and the like, and polymer particles made of these copolymers. preferable. It is preferable to increase the bonding force between the polymer chains constituting the polymer particles. Examples of means for strengthening the bonding force between polymer chains include a method using an interaction generated by hydrogen bonding and a method of generating a covalent bond.
  • 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 (such as styrene sulfonic acid group) and the like.
  • the binder polymer preferably has at least a carboxyl group.
  • a preferable range of the copolymerization ratio of the monomers having these polar groups is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and more preferably 20 to 30% by mass with respect to 100% by mass of the polymer. % Is more preferable.
  • an epoxy compound As a means for generating a covalent bond, an epoxy compound, a blocked isocyanate, an isocyanate, a vinyl sulfone compound, an aldehyde compound, a methylol compound, a carboxyl, a hydroxyl group, a carboxyl group, a primary, secondary amino group, an acetoacetyl group, a sulfonic acid group, etc.
  • the method of making an acid anhydride etc. react is mentioned.
  • the polymer latex 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)).
  • the polymer latex for example, a material selected from the following can be neutralized with ammonia and emulsified.
  • Aqueous dispersion of polyethylene ionomer Chemipearl S120 (trade name) manufactured by Mitsui Chemicals, solid content 27%; Chemipearl S100 (trade name) manufactured by Mitsui Chemicals, Inc., solid content 27%; Chemipearl S111 (trade name) Mitsui Chemical Co., Ltd., solid content 27%; Chemipearl S200 (trade name) Mitsui Chemicals, Inc., solid content 27%; Chemipearl S300 (trade name) Mitsui Chemicals, Inc., solid content 35%; Chemipearl S650 ( Product name) Mitsui Chemicals, Inc., solid content 27%; Chemipearl S75N (trade name) Mitsui Chemicals, Inc., solid content 24%, Aqueous dispersion of polyether polyurethane: Hydran WLS-201 (trade name), manufactured by DIC Corporation, solid content 35%, Tg-50 ° C.
  • Tg is an abbreviation for Glass Transition Temperature (glass transition temperature)
  • Hydran WLS- 202 (trade name) manufactured by DIC Corporation, solid content 35%, Tg-50 ° C
  • hydran WLS-221 (trade name) manufactured by DIC Corporation, solid content 35%, Tg-30 ° C
  • hydran WLS-210 ( Product name) DIC Corporation, solid content 35%, Tg-15 ° C
  • Hydran WLS-213 (trade name) DIC Corporation, solid content 35%, Tg-15 ° C
  • Hydran WLI-602 (trade name) DIC Co., Ltd., solid content 39.5%, Tg-50 ° C .
  • Hydran WLI-611 (trade name) DIC Co., Ltd., solid Min 39.5%, Tg-15 °C
  • Ammonium acrylate copolymer Jurimer AT-210 (trade name) manufactured by Nippon Pure Chemical Co., Ltd .
  • Jurimer ET-410 (trade name) manufactured by Nippon Pure Chemical Co
  • the weight average molecular weight of the binder polymer is preferably 10,000 or more, more preferably 20,000 to 100,000.
  • the curable resin layer preferably contains a polymerizable compound, more preferably contains a polymerizable compound having an ethylenically unsaturated group, and further preferably contains a photopolymerizable compound having an ethylenically unsaturated group.
  • the polymerizable compound preferably has at least one ethylenically unsaturated group as a polymerizable group.
  • the polymerizable compound may have an epoxy group in addition to the ethylenically unsaturated group. More preferably, the polymerizable compound of the curable resin layer includes a compound having a (meth) acryloyl group.
  • a polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the polymerizable compound preferably includes a bifunctional polymerizable compound, more preferably includes a compound having two ethylenically unsaturated groups, and further preferably includes a compound having two (meth) acryloyl groups.
  • the polymerizable 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.) and the like can be preferably used.
  • the content of the bifunctional polymerizable compound is preferably in the range of 20 to 90% by mass and preferably in the range of 30 to 80% by mass with respect to all the polymerizable compounds contained in the curable resin layer. More preferably, it is in the range of 35 to 75% by mass.
  • At least one of the polymerizable compounds contains a carboxyl group because the carboxyl group of the binder polymer and the carboxyl group of the polymerizable compound can form a carboxylic acid anhydride in the curable resin layer.
  • a polymeric compound containing a carboxyl 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 content of the polymerizable compound containing a carboxyl group is preferably in the range of 1 to 50% by mass, preferably in the range of 1 to 30% by mass, with respect to all the polymerizable compounds contained in the curable resin layer. More preferably, the content is in the range of 5 to 15% by mass.
  • a urethane (meth) acrylate compound is included as a polymerizable compound.
  • the number of functional groups of the polymerizable group that is, the number of (meth) acryloyl groups is preferably 3 or more, more preferably 4 or more.
  • a commercially available compound can be used.
  • 8UX-015A manufactured by Taisei Fine Chemical Co., Ltd.
  • the content of the urethane (meth) acrylate compound is preferably 10% by mass or more, and more preferably 20% by mass or more, based on all polymerizable compounds contained in the curable resin layer.
  • the polymerizable compound may contain a trifunctional or higher functional polymerizable compound.
  • 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.
  • skeletons such as dipentaerythritol (tri / tetra / penta / hexa) acrylate, pentaerythritol (tri / tetra) acrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, isocyanuric acid acrylate, glycerin triacrylate, etc.
  • the polymerizable compound preferably has a long distance between (meth) acrylates. Specifically, dipentaerythritol (tri / tetra / penta / hexa) acrylate, pentaerythritol (tri / tetra) acrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate (AD-made by Shin-Nakamura Chemical Co., Ltd.) TMP, etc.), caprolactone-modified compounds of skeletal (meth) acrylate compounds such as isocyanuric acid acrylate (Nippon Kayaku KAYARAD DPCA, Shin-Nakamura Chemical A-9300-1CL, etc.), alkylene oxide-modified compounds (Nippon Kayaku) KAYARAD RP-1040, Shin-Nakamura Chemical Co., Ltd.
  • ATM-35E, A-9300, Daicel Ornex EBECRYL 135, etc.), ethoxylated glycerin triacrylate (Shin Nakamura Chemical Co., Ltd. A-GLY-9E) Etc.) can be preferably used.
  • 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 content of the trifunctional or higher functional polymerizable compound is preferably in the range of 3 to 50% by mass, preferably in the range of 5 to 30% by mass, with respect to all the polymerizable compounds contained in the curable resin layer. Is more preferable, and the range of 7 to 20% by mass is even more preferable.
  • the polymerizable compound used in the curable resin layer preferably has a weight average molecular weight of 200 to 3000, more preferably 250 to 2600, and still more preferably 280 to 2200.
  • the molecular weight of the polymerizable compound which is the minimum molecular weight is preferably 250 or more, more preferably 280 or more, and further preferably 300 or more.
  • the curable resin layer contains a polymerizable compound, and the ratio of the content of the polymerizable compound having a molecular weight of 300 or less to the content of all polymerizable compounds contained in the curable resin layer is preferably 30% or less. 25% or less is more preferable, and 20% or less is more preferable.
  • the curable resin layer preferably contains a polymerization initiator, and more preferably contains a photopolymerization initiator.
  • a polymerization initiator used for a curable resin layer There is no restriction
  • the polymerization initiator used for the curable resin layer for example, photopolymerization initiators described in paragraphs 0031 to 0042 of JP2011-95716A can be used.
  • polymerization initiators are contained with respect to the curable resin layer, and it is more preferable that 2 mass% or more is contained.
  • the polymerization initiator is preferably contained in an amount of 10% by mass or less, more preferably 5% by mass or less with respect to the curable resin layer, from the viewpoint of improving the patterning property.
  • the curable resin layer preferably contains a compound that can react with an acid by heating.
  • the compound capable of reacting with an acid by heating is not particularly limited as long as it is not contrary to the gist of the present invention.
  • the compound capable of reacting with an acid by heating is preferably a compound having a high reactivity with an acid after heating at a temperature exceeding 25 ° C., compared with the reactivity with an acid at 25 ° C.
  • the compound that can react with an acid by heating has a group that can react with an acid that is temporarily inactivated by a blocking agent, and the group derived from the blocking agent is dissociated at a predetermined dissociation temperature. preferable.
  • Examples of the compound capable of reacting with an acid by heating include a carboxylic acid compound, an alcohol compound, an amine compound, a blocked isocyanate (also called a blocked isocyanate), an epoxy compound, and the like, and is preferably a blocked isocyanate. .
  • the compound capable of reacting with an acid by heating having a hydrophilic group in the molecule is not particularly limited, and a known compound can be used.
  • the method for preparing the compound capable of reacting with an acid by heating having a hydrophilic group in the molecule is not particularly limited, but for example, it can be prepared by synthesis.
  • the compound having a hydrophilic group in the molecule and capable of reacting with an acid by heating is preferably a blocked isocyanate having a hydrophilic group in the molecule. Details of the compound capable of reacting with an acid by heating having a hydrophilic group in the molecule will be described in the explanation of the blocked isocyanate described later.
  • Block isocyanate means “a compound having a structure in which an isocyanate group of isocyanate is protected (masked) with a blocking agent”.
  • the initial Tg of the blocked isocyanate is preferably -40 ° C to 10 ° C, more preferably -30 ° C to 0 ° C.
  • the dissociation temperature of the blocked isocyanate is preferably 100 to 160 ° C, more 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 (compounds having a structure represented by —C ( ⁇ N—OH) — in the molecule such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, cyclohexanone oxime), and the like.
  • oxime compounds and pyrazole compounds are preferable, and the like.
  • the blocked isocyanate has an isocyanurate structure from the viewpoint of reducing brittleness of the film of the curable resin layer and ensuring adhesion to the substrate.
  • a blocked isocyanate having an isocyanurate structure can be prepared, for example, by isocyanurating hexamethylene diisocyanate.
  • blocked isocyanates having an isocyanurate structure compounds having an oxime structure using an oxime-based compound as a blocking agent tend to have a dissociation temperature within a preferable range and less development residues than compounds having no oxime structure. It is preferable from the viewpoint of easy handling.
  • the number of blocked isocyanate groups of the blocked isocyanate per molecule is preferably 1 to 10, more preferably 2 to 6, and further preferably 3 to 4.
  • blocked isocyanate a blocked isocyanate compound described in paragraphs 0074 to 0085 of JP-A-2006-208824 may be used, and the contents of this publication are incorporated herein.
  • Specific examples of the blocked isocyanate include the following compounds.
  • the blocked isocyanate used in the present invention is not limited to the following specific examples.
  • blocked isocyanate can also be mentioned as the blocked isocyanate.
  • 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, T307-B80E which is a hexamethylene diisocyanate-based blocked isocyanate compound. 04 (all manufactured by Asahi Kasei Chemicals Corporation).
  • the blocked isocyanate having a hydrophilic group in the molecule is preferably a blocked isocyanate in which at least a part of the isocyanate group is an aqueous isocyanate group to which a hydrophilic group is added.
  • a blocking agent sometimes referred to as an amine compound
  • a blocked isocyanate having a hydrophilic group in the molecule can be obtained.
  • the reaction method include a method of adding a hydrophilic group to a part of the isocyanate group of the polyisocyanate by a chemical reaction.
  • the hydrophilic group of the compound capable of reacting with an acid by heating is not particularly limited, and specific examples include a nonionic hydrophilic group and a cationic hydrophilic group.
  • the compound etc. which added ethylene oxide and propylene oxide to the hydroxyl group of alcohol such as methanol, ethanol, butanol, ethylene glycol, or diethylene glycol
  • the hydrophilic group of a compound that can react with an acid by heating having a hydrophilic group in the molecule is preferably an ethylene oxide chain or a propylene oxide chain.
  • These compounds have active hydrogens that react with isocyanate groups and can thereby be added to isocyanate groups.
  • monoalcohols that can be dispersed in water with a small amount of use are preferable.
  • the number of ethylene oxide chains or propylene oxide chains added in the molecule is preferably 4 to 30, and more preferably 4 to 20. If the addition number is 4 or more, the water dispersibility tends to be further improved. Moreover, if the addition number is 30 or less, the initial Tg of the obtained blocked isocyanate tends to be further improved.
  • the cationic hydrophilic group is added by a method using a compound having both a cationic hydrophilic group and an active hydrogen that reacts with an isocyanate group, and by introducing a functional group such as a glycidyl group into the polyisocyanate in advance. Examples thereof include a method of reacting a specific compound such as sulfide or phosphine with this functional group.
  • the former method is easy. Although it does not specifically limit as active hydrogen which reacts with an isocyanate group, Specifically, a hydroxyl group, a thiol group, etc. are mentioned.
  • the compound having both a cationic hydrophilic group and active hydrogen that reacts with an isocyanate group is not particularly limited, and specific examples include dimethylethanolamine, diethylethanolamine, diethanolamine, and methyldiethanolamine.
  • the tertiary amino group thus introduced can be quaternized with dimethyl sulfate, diethyl sulfate or the like.
  • the equivalent ratio of the isocyanate group to which a hydrophilic group is added and the blocked isocyanate group is preferably 1:99 to 80:20, more preferably 2:98 to 50:50, and 5:95 to 30. : 70 is more preferable.
  • the above preferable range is preferable from the viewpoint of increasing isocyanate reactivity and reducing development residue.
  • the blocked isocyanate having a hydrophilic group in the molecule and the synthesis method thereof the aqueous blocked polyisocyanate described in paragraphs 0010 to 0045 of JP-A No. 2014-065833 can be preferably used. Embedded in the book.
  • the addition reaction of the hydrophilic group and the blocking reaction of the isocyanate group can be performed in the presence of a synthesis solvent.
  • the synthesis solvent preferably contains no active hydrogen, and examples thereof include dipropylene glycol monomethyl ether and propylene glycol monomethyl ether acetate methoxypropyl acetate.
  • the compound having a hydrophilic group is preferably added in an amount of 1 to 100% by weight, preferably 2 to 80% by weight, based on the polyisocyanate. Is more preferable.
  • the blocking agent is preferably added in an amount of 10 to 100% by mass, more preferably 20 to 99% by mass relative to the polyisocyanate.
  • the blocked isocyanate used in the transfer film preferably has a weight average molecular weight of 200 to 3000, more preferably 250 to 2600, and even more preferably 280 to 2200.
  • the curable resin layer may 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 polymerizable 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, and particularly preferably not contained.
  • the curable resin layer does not contain metal oxide particles, a case where metal oxide particles are included is also included in the present invention.
  • the metal oxide particles include ZrO 2 particles, Nb 2 O 5 particles, and TiO 2 particles.
  • the refractive index of the metal oxide particles is preferably higher than the refractive index of a composition made of a material obtained by removing the metal oxide particles from the curable resin layer.
  • the refractive index of the metal oxide particles is preferably higher than the refractive index of the curable resin layer not including the metal oxide particles.
  • the metal of the metal oxide particles 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.
  • As the titanium oxide a rutile type having a high refractive index is particularly preferable.
  • the surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.
  • the average primary particle diameter of the metal oxide particles is preferably 1 to 200 nm, and more 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.
  • the longest side is the diameter.
  • the metal oxide particles may be used alone or in combination of two or more.
  • additives may be further used for the curable resin layer.
  • additives include surfactants described in paragraph 0017 of Japanese Patent No. 4502784, paragraphs 0060 to 0071 of JP-A-2009-237362, known fluorosurfactants, and paragraphs of Japanese Patent No. 4502784.
  • thermal polymerization inhibitors described in 0018, and other additives described in paragraphs 0058 to 0071 of JP-A No. 2000-310706.
  • the additive preferably used for the curable resin layer include Megafac F-551 (manufactured by DIC Corporation), which is a known fluorosurfactant.
  • the curable resin layer of the transfer film is a negative type material
  • the curable resin layer of the transfer film may be a positive type material.
  • the transfer film may have a second resin layer.
  • the transfer film preferably has a second resin layer between the protective film and the curable resin layer from the viewpoint that two or more resin layers can be laminated at once from the transfer film and productivity can be improved. More preferably, the curable resin layer and the second resin layer are in direct contact.
  • the second resin layer preferably contains particles from the viewpoint of reducing transfer defects.
  • the second resin layer is preferably formed by applying a second resin layer forming coating solution containing particles.
  • the second resin layer is preferably curable.
  • the double bond consumption rate of the second resin layer is, for example, by using a Fourier transform infrared spectrophotometer (FT-IR) or the like, and the second resin layer immediately after coating and drying and the second resin layer in the transfer film. For the intercept, peak intensities A 2 and B 2 derived from C ⁇ C bonds at a specific wavelength can be obtained and calculated by the following formula.
  • Double bond consumption rate of second resin layer ⁇ 1- (B 2 / A 2 ) ⁇ ⁇ 100% Photolithography is practically required to be performed at least on a curable resin layer that is a layer closer to the outside than the second resin layer after transfer.
  • the second resin layer that becomes a layer closer to the inside than the curable resin layer after the transfer may not have photolithographic properties.
  • the curable resin layer since the curable resin layer is curable in the state of a transfer film, the curable resin layer that becomes a layer closer to the outside than the second resin layer after transfer has photolithography.
  • the second resin layer may be thermosetting, photocurable, thermosetting and photocurable. Among these, it is preferable that the second resin layer is at least a thermosetting resin layer from the viewpoint of thermosetting after transfer and imparting film reliability, and is a thermosetting resin layer and a photocurable resin layer.
  • the second resin layer may not be cured in the state of the transfer film, in which case the double bond consumption rate of the curable resin layer is 0%. .
  • the double resin consumption rate of the second resin layer may be cured in the state of the transfer film.
  • the combined consumption rate is preferably more than 0% and less than 10%. From the viewpoint of imparting photolithographic properties to the second resin layer, the double bond consumption rate of the second resin layer is preferably less than 10%, and more preferably 0%.
  • the refractive index of the cured resin layer n 1 and the refractive index n 2 of the second resin layer preferably satisfies the following formula 1.
  • the transparent electrode pattern preferably Indium Tin Oxide; including a metal oxide such as ITO
  • the transfer film satisfies Formula 1: n 1 ⁇ n 2, thereby reducing the refractive index difference between the transparent electrode pattern and the second resin layer and the refractive index difference between the second resin layer and the curable resin layer.
  • a transfer film can be obtained.
  • the transfer film satisfies the above formula 1
  • the layer fraction is improved when the method for producing a transfer film described later is used.
  • the concealability of the transparent electrode pattern can be improved by the above-described mechanism, and photolithography is performed after the refractive index adjustment layer (that is, the curable resin layer and the second resin layer) is transferred from the transfer film onto the transparent electrode pattern. Can be developed into a desired pattern.
  • the refractive index of the second resin layer is preferably higher than the refractive index of the curable resin layer.
  • the value of n 2 ⁇ n 1 is preferably 0.03 to 0.30, and more preferably 0.05 to 0.20.
  • the refractive index n 2 of the second resin layer is preferably 1.60 or more.
  • the refractive index of the second resin layer needs to be adjusted according to the refractive index of the transparent electrode pattern, and the upper limit is not particularly limited, but is preferably 2.1 or less, and is 1.78 or less. More preferably.
  • the refractive index n 2 of the second resin layer is preferably 1.60 ⁇ n 2 ⁇ 1.75.
  • the refractive index of the second resin layer may be 1.74 or less.
  • the refractive index n 2 of the second resin layer is 1.7. It is preferable that it is 1.85 or more.
  • the method for controlling the refractive index of the second resin layer is not particularly limited, but a resin layer having a desired refractive index is used alone, or a 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.
  • the thickness of the second resin layer is preferably 500 nm or less, and more preferably 110 nm or less.
  • the lower limit of the thickness of the second resin layer is preferably 20 nm or more.
  • the thickness of the second resin layer is more preferably 55 to 100 nm, particularly preferably 60 to 100 nm, and particularly preferably 70 to 100 nm.
  • T 2 represents the average thickness of the second resin layer.
  • the term “the thickness of the second resin layer” refers to “the average thickness T 2 of the second resin layer” unless otherwise specified.
  • the second resin layer is preferably alkali-soluble.
  • the second resin layer may be a negative material or a positive material, and is preferably a negative material.
  • the second resin layer preferably contains a resin having an acid group, a monomer having an acid group, particles, and a metal oxidation inhibitor.
  • the second resin layer may contain another binder polymer, a polymerizable compound, and a polymerization initiator.
  • the second resin layer may contain an additive.
  • 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 a resin having 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 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 used for the second 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.). Among these, those which are soluble in an organic solvent and can be developed using a weak alkaline aqueous solution are more preferable. As the acid group of the resin having an acid group, a carboxyl group is more 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 linear organic polymer the polymer having a carboxylic acid in the side chain is preferable.
  • the polymer having a carboxylic acid in the side chain is preferable.
  • JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 Poly (meth) acrylic acid, methacrylic acid copolymer, acrylic acid copolymer, itacone as described in JP-A No. 46-2121 and JP-B-56-40824.
  • Acid copolymer crotonic acid copolymer, maleic acid copolymer such as styrene / maleic acid, partially esterified maleic acid copolymer, etc., and carboxylic acid in side chain such as carboxyalkyl cellulose and carboxyalkyl starch Acid cellulose derivatives, polymers with hydroxyl groups, acid anhydrides, etc., and (meth) acryloyl groups in the side chain High molecular polymer having a reactive functional group may also be mentioned as preferred.
  • the resin having an acid group is preferably an acrylic resin.
  • 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 alone or in combination of two or more.
  • 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 more preferably a benzyl (meth) acrylate / (meth) acrylic acid copolymer or a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers.
  • a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate is also preferably used as the resin having an acid group.
  • Resins having an acid group can be mixed and used in an arbitrary amount.
  • the resin having an acid group includes 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3- Phenoxypropyl acrylate / polymethyl methacrylate 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.
  • an acrylic resin having an acid group is preferable, a copolymer resin of (meth) acrylic acid / vinyl compound is preferable, and (meth) acrylic acid / (meta It is particularly preferable that it is a copolymer resin of allyl acrylate.
  • acrylic resin includes both methacrylic resin and acrylic resin, and (meth) acrylic similarly includes methacrylic and acrylic.
  • the weight average molecular weight of the resin having an acid group is preferably 10,000 or more, and more preferably 20,000 to 100,000.
  • the content of the resin having an acid group with respect to the second resin layer is preferably 10 to 80% by mass, more preferably 15 to 65% by mass, and further preferably 20 to 50% by mass.
  • acrylic monomers such as (meth) acrylic acid and derivatives thereof, and the following monomers can be preferably used.
  • a bifunctional alkali-soluble radically polymerizable monomer as needed.
  • monomers having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239842 can be preferably used, and the contents of this publication are incorporated in the present invention.
  • the monomer which has an acid group among the polymeric compounds quoted as a polymeric compound used for a curable resin layer can also be used preferably.
  • a polymerizable compound containing a carboxyl group is preferable, and acrylic monomers such as (meth) acrylic acid and derivatives thereof can be more preferably used.
  • the acrylic monomer includes both a methacrylic monomer and an acrylic monomer.
  • the content of the monomer having an acid group is preferably 1 to 50% by mass, more preferably 3 to 20% by mass, and further preferably 6 to 15% by mass with respect to the resin having an acid group. .
  • the second resin layer preferably contains particles from the viewpoint of controlling adhesion with the protective film and reducing transfer defects.
  • the second resin layer preferably contains 60 to 90% by mass of particles with respect to the total solid content of the second resin layer from the viewpoint of reducing transfer defects, and more preferably 65 to 90% by mass. 70 to 85% by mass is more preferable.
  • the second resin layer contains particles in an amount of 60% by mass or more based on the total solid content of the second resin layer, and the second resin layer (and / or the curable resin layer) peeled off the protective film. In view of reducing the adhesiveness to such an extent that transfer defects transferred to the protective film can be reduced.
  • the interface between the protective film and the second resin layer (and / or the curable resin layer) is that the second resin layer contains 90% by mass or less of particles with respect to the total solid content of the second resin layer. From the viewpoint of maintaining adhesiveness to such an extent that generation of bubbles can be suppressed.
  • the refractive index of the particles is preferably higher than the refractive index of a composition made of a material obtained by removing the particles from the second resin layer. In other words, the refractive index of the particles is preferably higher than the refractive index of the second resin layer that does not include particles.
  • the particles contained in the second resin layer are preferably particles having a refractive index of 1.50 or more from the viewpoint of the concealability of the transparent electrode pattern.
  • the second resin layer preferably contains particles having a refractive index of 1.55 or more, more preferably contains particles having a refractive index of 1.70 or more, and contains particles of 1.90 or more. It is particularly preferable that it contains particles of 2.00 or more.
  • the refractive index of the particles contained in the second resin layer is a refractive index in light having a wavelength of 400 nm to 750 nm.
  • the refractive index of light having a wavelength of 400 nm 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.
  • the average refractive index is a value obtained by dividing the sum of the measured values of the refractive index for each light having a wavelength in the above range by the number of measurement points.
  • the second resin layer preferably contains 60 to 90% by mass of particles having a refractive index of 1.50 or more based on the total solid content of the second resin layer.
  • the particles having a refractive index of 1.50 or more are more preferably metal oxide particles from the viewpoint of adjusting the refractive index and light transmittance.
  • the second resin layer can contain metal oxide particles at an arbitrary ratio depending on the resin used, the type and content of the polymerizable monomer, the type of metal oxide particles used, and the like. There is no restriction
  • the metal oxide particles mentioned in the curable resin layer described above can also be used in the second resin layer.
  • the second resin layer contains at least one of zirconium oxide particles (ZrO 2 particles), Nb 2 O 5 particles, and titanium oxide particles (TiO 2 particles).
  • the metal oxide particles are more preferably zirconium oxide particles or titanium oxide particles, and even more preferably zirconium oxide particles.
  • the particles commercially available products may be used.
  • nano-use OZ-S30M Nano-use OZ-S30M (Nissan Chemical Industry Co., Ltd.) can be preferably used.
  • the content of the zirconium oxide particles is the total amount of the second resin layer from the viewpoint of providing appropriate adhesion to the protective film and reducing bubbles and transfer defects.
  • the metal oxide particles are preferably contained in an amount of 30 to 70% by mass with respect to the total solid content of the second resin layer. More preferably, the content is 40% by mass or more and less than 60% by mass.
  • the metal oxide particles may be used alone or in combination of two or more.
  • the second resin layer preferably contains a metal oxidation inhibitor.
  • the second resin layer contains a metal oxidation inhibitor
  • the second resin layer is laminated on a transparent substrate (the transparent substrate preferably includes a transparent electrode pattern, a metal wiring portion, etc.) It becomes possible to surface-treat the metal wiring portion that is in direct contact with the second resin layer. It is considered that the protection of the metal wiring portion provided by the surface treatment is effective even after the second resin layer (and the support-side functional layer) is removed.
  • the metal oxidation inhibitor used in the present invention 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 preferable, and the aromatic ring containing the nitrogen atom is more preferably an imidazole ring or a condensed ring of an imidazole ring and another aromatic ring.
  • the other aromatic ring may be a carbocyclic ring or a heterocyclic ring, but is preferably a carbocyclic ring, more preferably a benzene ring or a naphthalene ring, and further preferably a benzene ring.
  • Preferable metal oxidation inhibitors include imidazole, benzimidazole, tetrazole, mercaptothiadiazole, and benzotriazole, and imidazole, benzimidazole, and benzotriazole are more preferable.
  • Commercially available products may be used as the metal oxidation inhibitor, and for example, BT120 manufactured by Johoku Chemical Industry Co., Ltd. containing benzotriazole can be preferably used.
  • the content of the metal oxidation inhibitor is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass with respect to the total mass of the second resin layer. More preferably, it is ⁇ 5% by mass.
  • the second resin layer contains a polymerizable compound such as a photopolymerizable compound or a thermopolymerizable compound from the viewpoint of curing and increasing the strength of the film.
  • the second resin layer may contain only the above-mentioned monomer having an acid group as a polymerizable compound, or may contain other polymerizable compound other than the above-mentioned monomer having an acid group.
  • the polymerizable compound used in the second resin layer the polymerizable 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 polymerizable 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%.
  • a water-soluble polymerizable compound represented by the following structural formula 1 and a pentaerythritol tetraacrylate mixture (NK ester A-TMMT Shin-Nakamura Chemical Co., Ltd.) ), Containing about 10% triacrylate as an impurity), a mixture of pentaerythritol tetraacrylate and triacrylate (NK ester A-TMM3LM-N, Shin-Nakamura Chemical Co., Ltd., triacrylate 37%), pentaerythritol tetraacrylate and Mixture of triacrylate (NK Ester A-TMM-3L made by Shin-Nakamura Chemical Co., Ltd., triacrylate 55%), mixture of pentaerythritol tetraacrylate and triacrylate (NK Ester A-TMM3 made by Shin-Nakamura Chemical Co., Ltd.) , Triacrylate 5 7%), t
  • the alcohol dispersion of the metal oxide particles may be soluble in a mixed solvent of lower alcohol having 1 to 3 carbon atoms such as methanol and water. It is preferable when the liquid is used in combination with an aqueous resin composition.
  • the polymerizable compound having solubility in water or a mixed solvent of a lower alcohol having 1 to 3 carbon atoms and water include a monomer having a hydroxyl group, an ethylene oxide, a polypropylene oxide, and a phosphate group in the molecule. Monomers can be used.
  • Examples of the polymerizable compound having solubility in a mixed solvent of a lower alcohol having 1 to 3 carbon atoms and water include Kayarad RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and Aronix TO-2349 (Toagosei Co., Ltd.). )), Polymerizable monomer A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.), A-GLY-20E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like are preferable.
  • the polymerizable compound is soluble in a mixed solvent of a lower alcohol having 1 to 3 carbon atoms and water means that the polymerizable compound is dissolved in a mixed solvent of alcohol and water by 0.1% by mass or more.
  • the content of the polymerizable compound is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and preferably 0 to 5% by mass with respect to the total solid content of the second resin layer. More preferably.
  • the polymerization initiator used for the second resin layer preferably has solubility in water or a mixed solvent of water and a lower alcohol having 1 to 3 carbon atoms and water.
  • a polymerization initiator used for the second resin layer IRGACURE 2959 or a polymerization initiator represented by the following structural formula 2 can be used.
  • the content of the polymerization initiator is preferably 0 to 5% by mass and preferably 0 to 1% by mass with respect to the total solid content of the resin composition used for forming the second resin layer. More preferred is 0 to 0.5% by mass.
  • the second resin layer may contain another binder polymer having no acid group. There is no restriction
  • the binder polymer used for the above-mentioned curable resin layer can be used.
  • the second resin layer may contain an additive.
  • 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 inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Furthermore, other additives described in paragraphs 0058 to 0071 of JP-A No. 2000-310706 can be mentioned.
  • the additive preferably used for the second resin layer include Megafac F-444 (manufactured by DIC Corporation), which is a known fluorosurfactant.
  • the second resin layer of the transfer film is a negative type material
  • the second resin layer of the transfer film may be a positive type material.
  • the second resin layer of the transfer film is a positive type material, for example, the material described in JP-A-2005-221726 can be used for the second resin layer.
  • the transfer film may have other arbitrary layers in addition to the temporary support, the curable resin layer, the second resin layer, and the protective film as long as the effects of the present invention are not impaired.
  • Other optional layers may include a thermoplastic resin layer and an intermediate layer.
  • thermoplastic resin layer The transfer film can also be provided with a thermoplastic resin layer between the temporary support and the curable resin layer.
  • thermoplastic resin layer reference can be made to the thermoplastic resin layers described in paragraphs 0041 to 0047 of JP-A-2014-108541. The contents of this publication are incorporated herein.
  • the transfer film may be provided with an intermediate layer between the thermoplastic resin layer and the curable resin layer.
  • the intermediate layer is described as “separation layer” in JP-A-5-72724.
  • the manufacturing method of a transfer film is not specifically limited, It can manufacture by a well-known method.
  • a step of forming a curable resin layer on the temporary support, and a step of forming a protective film on the curable resin layer It is preferable to have.
  • the process of forming a curable resin layer on a temporary support body when manufacturing the transfer film which has a 2nd resin layer, the process of forming a 2nd resin layer on a curable resin layer, 2nd And a step of forming a protective film on the resin layer.
  • the step of forming the curable resin layer is preferably a step of applying the organic solvent-based resin composition on the temporary support.
  • the step of forming the second resin layer is a step of forming the second resin layer directly on the curable resin layer.
  • the step of forming the second resin layer is preferably a step of applying an aqueous resin composition from the viewpoint of improving the layer fraction.
  • the aqueous resin composition on the curable resin layer obtained by the organic solvent-based resin composition to form the second resin layer, the second resin without curing the curable resin layer. Even when the layers are formed, interlayer mixing does not occur, and the layer fraction is improved.
  • the aqueous resin composition used for forming the second resin layer may be applied to form the second resin layer.
  • the double bond consumption rate of the curable resin layer is 0%.
  • the second resin layer may be formed after the curable resin layer is cured.
  • the double bond consumption rate is cured within a range of less than 10%, and the adhesiveness of the curable resin layer is reduced within a range in which photolithography can be sufficiently maintained, and then the second resin.
  • a layer or protective film may be provided.
  • the double bond consumption rate of the curable resin layer is more than 0% and less than 10%.
  • a method for curing the curable resin layer a method similar to the method for curing the curable resin layer after transfer in the method for producing a laminate described later can be used. Hereinafter, preferred embodiments of each step will be described.
  • the manufacturing method of a transfer film includes the process of forming a curable resin layer on a temporary support body.
  • the step of forming the curable resin layer is preferably a step of applying the organic solvent-based resin composition on the temporary support.
  • 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 (1-methoxy-2-propyl acetate), cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.
  • an organic solvent may be used individually by 1 type and can also use 2 or more types together.
  • the organic solvent-based resin composition used for forming the curable resin layer preferably includes a binder polymer, a polymerizable compound, and a polymerization initiator. Furthermore, since the organic solvent-based resin composition used for forming the curable resin layer contains a surfactant containing fluorine atoms (also referred to as a fluorine-based surfactant), the curable resin layer is cured without being cured. Even if the second resin layer is formed, interlayer mixing does not occur, and the thickness uniformity of the second resin layer is improved.
  • a surfactant containing fluorine atoms also referred to as a fluorine-based surfactant
  • the adhesiveness of a 2nd resin layer and a transparent electrode pattern becomes favorable.
  • Step of forming the second resin layer It is preferable that the manufacturing method of a transfer film includes the process of forming a 2nd resin layer.
  • the step of forming the second resin layer is preferably a step of applying the aqueous resin composition. 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 resistance of the transfer film. Specifically, 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 is preferably used as the aqueous resin composition.
  • ammonia having a lower boiling point than water is obtained from an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group. Is easy to volatilize. Therefore, an acid group can be generated (regenerated) from the ammonia salt state, and a monomer having an acid group or a resin having an acid group can be present in the second resin layer. Since the monomer having an acid group or the resin having an acid group constituting the second resin layer in which the acid group has been generated does not dissolve in water, the moisture resistance of the transfer film can be improved.
  • the aqueous resin composition refers to a resin composition that can be dissolved in an aqueous solvent.
  • aqueous solvent water or a mixed solvent of water and a lower alcohol having 1 to 3 carbon atoms and water is preferable.
  • the solvent of the aqueous resin composition used for forming the second resin layer preferably contains water and an alcohol having 1 to 3 carbon atoms, and has 1 to 3 carbon atoms. It is more preferable to include water or a mixed solvent having an alcohol / water mass ratio of 20/80 to 80/20.
  • 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 mass ratio (mass% ratio) of methanol / water is preferably 20/80 to 80/20, and 30/70 More preferably, it is ⁇ 70 / 30, and particularly preferably 40/60 to 70/30.
  • the pH (Power of Hydrogen) at 25 ° C. of the aqueous resin composition is preferably 7 to 12, more preferably 7 to 10, and particularly preferably 7 to 8.5.
  • 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 2nd resin layer is at least one among thermosetting and photocurability.
  • the second resin layer may be laminated without being cured after the curable resin layer is laminated in the transfer film manufacturing method.
  • the layer fraction is improved and the transparent electrode pattern concealing property can be improved.
  • the laminated body described later further transfers the curable resin layer and the second resin layer from the obtained transfer film onto the transparent electrode pattern at the same time, and at least after transfer from the second resin layer by photolithography.
  • the curable resin layer that becomes a layer close to the outside can be developed into a desired pattern.
  • An embodiment in which the second resin layer is curable is more preferable.
  • the curable resin layer and the second resin layer are simultaneously transferred onto the transparent electrode pattern, and then developed into a desired pattern by photolithography at the same time. it can.
  • Providing a protective film without curing the second resin layer is preferable from the viewpoint of imparting photolithographic properties.
  • the double bond consumption rate of the second resin layer is 0%.
  • the second resin layer is cured within a range where the double bond consumption rate is less than 10%, and the adhesiveness of the curable resin layer is reduced within a range where the photolithography property can be sufficiently maintained, and then a protective film is provided. May be.
  • the double bond consumption rate of the second resin layer is more than 0% and less than 10%.
  • the aqueous resin composition used for forming the second resin layer 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 in the second resin layer is preferably an acrylic monomer having an acid group or an ammonium salt of an acrylic resin.
  • the step of forming the second resin layer comprises dissolving a monomer having an acid group or a resin having an acid group in an aqueous ammonia solution, and including a monomer or a resin in which at least a part of the acid group is ammonium chlorided. It is preferable to include the process of preparing.
  • the aqueous resin composition used for forming the second resin layer contains an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group, a binder polymer, and light or heat. It preferably contains a polymerizable compound and a light or thermal polymerization initiator.
  • 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. It is preferable that 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. .
  • the preferable range of detailed conditions of the step of heating the applied aqueous resin composition is shown below. Heating and drying 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 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.
  • the manufacturing method of a transfer film includes the process of forming a protective film.
  • a protective film There is no restriction
  • the manufacturing method of a transfer film includes the process of forming a roll.
  • the transfer film which formed the protective film can mention the method of winding up in roll shape so that a protective film may become an outer side.
  • thermoplastic resin layer Before the curable resin layer is formed on the temporary support, a step of further forming a thermoplastic resin layer may be included.
  • a step of forming an intermediate layer between the thermoplastic resin layer and the curable resin layer may be included.
  • a solution thermoplastic resin coating solution
  • a thermoplastic organic polymer and additives are dissolved is applied onto a temporary support, dried, and heated. It is preferable to provide a plastic resin layer.
  • a coating resin for a curable resin layer prepared by using a solvent that does not dissolve the intermediate layer is further applied on the intermediate layer and dried to laminate the curable 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 used for an electrode protective film of a capacitive input device, and is preferably used for a transparent insulating layer or a transparent protective layer among electrode protective films.
  • the curable resin layer may be in an uncured state. In that case, transfer for forming a laminated pattern of the electrode protective film of the capacitive input device on the transparent electrode pattern by photolithography. It can be used as a film, and is more preferably used as a transfer film for forming a laminated pattern of a refractive index adjusting layer and an overcoat layer (transparent protective layer).
  • 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.
  • An electrode protective film of capacitive input device is a film
  • the electrode protective film of the capacitive input device of the present invention is obtained by removing the protective film from the transfer film of the present invention.
  • the electrode protective film of the capacitive input device is preferably a film obtained by removing the protective film and the temporary support from the transfer film. More preferably, the electrode protective film of the capacitance type input device is obtained by transferring a curable resin layer from a transfer film onto a transparent electrode pattern and then curing the curable resin layer.
  • the electrode protective film of the capacitance type input device is preferably one obtained by photocuring a curable resin layer, and more preferably one obtained by photocuring and heat treatment.
  • the laminated body of this invention has the board
  • the electrode of the capacitive input device may be a transparent electrode pattern or a lead wiring.
  • the electrode of the capacitive input device is preferably an electrode pattern, and more preferably a transparent electrode pattern.
  • the laminate has a substrate including electrodes of the capacitive input device and a curable resin layer formed on the substrate.
  • the laminate preferably has at least a substrate, a transparent electrode pattern, and a curable resin layer.
  • the laminate has a substrate, a transparent electrode pattern, a second resin layer disposed adjacent to the transparent electrode pattern, and a curable resin layer disposed adjacent to the second resin layer. Is more preferable.
  • the laminate has a substrate, a transparent electrode pattern, a second resin layer disposed adjacent to the transparent electrode pattern, and a curable resin layer disposed adjacent to the second resin layer.
  • the refractive index of the second resin layer is more preferably higher than the refractive index of the curable resin layer, and the refractive index of the second resin layer is particularly preferably 1.6 or more.
  • the laminate may further include a transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm on the opposite side of the transparent electrode pattern on which the second resin layer is formed. From the viewpoint of further improving the concealability of the electrode pattern, it is preferable.
  • the term “transparent film” unless otherwise specified refers to the “transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm”.
  • the laminate preferably further has a transparent substrate on the side opposite to the side where the transparent electrode pattern of the transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm is formed.
  • FIG. 11 shows an example of the structure of the laminate.
  • the transparent substrate 1, the transparent film 11 preferably having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm
  • the transparent electrode pattern 4 the second resin layer 12, and curing
  • a region 21 in which the conductive resin layer 7 is laminated in this order is provided in the plane.
  • the laminate 13 in FIG. 11 includes a region 22 in which the transparent substrate 1, the transparent film 11, the second resin layer 12, and the curable resin layer 7 are stacked in this order (that is, a transparent electrode). It is shown to include a non-pattern region 22) where no pattern is formed.
  • the laminate 13 includes a region 21 in which the transparent substrate 1, the transparent film 11, the transparent electrode pattern 4, the second resin layer 12, and the curable 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 transparent substrate of the laminate. Therefore, the transparent electrode pattern 4, the second resin layer 12, and the curable resin layer 7 include in the plane the region in which the transparent electrode pattern 4, the second resin layer 12, and the curable resin layer 7 are laminated in this order. This means that an orthographic projection of the region 7 in this order on the plane parallel to the transparent substrate of the laminate exists in the plane parallel to the transparent substrate of the laminate.
  • the transparent electrode pattern is in two directions intersecting (for example, orthogonal to) the first direction and the second direction (for example, the row direction and the column direction).
  • Each may be provided as a first transparent electrode pattern and a second transparent electrode pattern (see, for example, FIG. 3).
  • the transparent electrode pattern in the laminate 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 is not limited to the second transparent electrode pattern 4 in the capacitive input device, and may be represented by a pad portion 3a of the first transparent electrode pattern 3, for example.
  • the laminate preferably includes a non-pattern region where a transparent electrode pattern is not formed.
  • the non-pattern region means a region where the transparent electrode pattern 4 is not formed.
  • FIG. 11 shows an aspect in which the stacked body includes the non-pattern region 22.
  • the laminated body preferably includes an in-plane region in which the transparent substrate, the transparent film, and the second resin layer are laminated in this order in at least a part of the non-pattern region 22 where the transparent electrode pattern is not formed.
  • the transparent film and the second resin layer are preferably adjacent to each other in a region where the transparent substrate, the transparent film, and the second resin layer are laminated in this order.
  • the laminated body is used for a capacitive input device described later.
  • the mask layer 2, the insulating layer 5, or another conductive element 6 in FIG. 1A can be laminated.
  • the transparent substrate and the transparent film are preferably adjacent to each other.
  • FIG. 11 shows a mode in which the transparent film 11 is laminated adjacently on the transparent substrate 1.
  • a third transparent film may be laminated between the transparent substrate and the transparent film as long as it does not contradict the gist of the present invention.
  • the laminate preferably has a transparent film thickness of 55 to 110 nm, more preferably 60 to 110 nm, and particularly preferably 70 to 90 nm.
  • the transparent film 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, but may have a tapered shape as shown in FIG. 11, for example, the surface on the transparent substrate side is more than the surface on the opposite side. May have a wide taper shape.
  • the angle of the end of the transparent electrode pattern (hereinafter also referred to as a taper angle) is preferably 30 ° or less, preferably 0.1 to 15 °. More preferably, it is more preferably 0.5 to 5 °.
  • the method for measuring the taper angle in the present specification can be obtained by taking a photomicrograph of the end of the transparent electrode pattern, 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 even more 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 preferably includes a region where the transparent electrode pattern and the second resin layer are adjacent to each other.
  • the transparent electrode pattern, the second resin layer, and the curable resin layer are adjacent to each other in the region 21 in which the transparent electrode pattern, the second resin layer, and the curable resin layer are laminated in this order. It is shown.
  • both the transparent electrode pattern and the non-pattern region 22 where the transparent electrode pattern is not formed are continuously or directly covered with another layer by the transparent film and the second resin layer.
  • “continuously” means that the transparent film and the second resin layer are not a pattern film but a continuous film. That is, it is preferable that the transparent film and the second resin layer have no opening from the viewpoint of making it difficult to visually recognize the transparent electrode pattern.
  • the transparent electrode pattern and the non-pattern region 22 are directly covered by the transparent film and the second resin layer without interposing other layers.
  • FIG. 11 shows an aspect in which the second resin layer 12 is laminated.
  • the second resin layer 12 is laminated over a region where the transparent electrode pattern 4 is not laminated on the transparent film 11 and a region where the transparent electrode pattern 4 is laminated. That is, the second resin layer 12 is adjacent to the transparent film 11, and the second resin layer 12 is adjacent to the transparent electrode pattern 4.
  • the edge part of the transparent electrode pattern 4 is a taper shape, it is preferable that the 2nd resin layer 12 is laminated
  • FIG. 11 shows an aspect in which the curable resin layer 7 is laminated on the surface of the second resin layer 12 opposite to the surface on which the transparent electrode pattern is formed.
  • the stacked body has a substrate including electrodes of the capacitive input device. It is preferable that the substrate including the electrodes of the capacitive input device is a separate member.
  • the substrate is preferably a transparent substrate.
  • the transparent substrate is preferably a glass substrate or a transparent film substrate, and more preferably a transparent film substrate.
  • the refractive index of the transparent substrate is preferably 1.5 to 1.55, and more preferably 1.5 to 1.52.
  • the transparent substrate may be composed of a light-transmitting substrate such as a glass substrate, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used.
  • the transparent substrate materials described in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.
  • a transparent film substrate it is more preferable to use one that is not optically distorted or one that has high transparency.
  • Specific examples of the transparent film substrate include a transparent film substrate containing polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, or a cycloolefin resin.
  • 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 and conductive metal oxide film such as ITO or IZO, or a metal film. Examples of such metal oxide films and metal films include ITO films, metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo, and metal oxide films such as SiO 2 . At this time, the thickness of each element can be 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 1st transparent electrode pattern 3, the 2nd transparent electrode pattern 4, and another electroconductive element 6 use the photosensitive film which has the electroconductive photocurable resin layer using an electroconductive fiber. It can also be manufactured.
  • the transparent electrode pattern is preferably an ITO film.
  • the transparent electrode pattern is more preferably an ITO film having a refractive index of 1.75 to 2.1.
  • the laminate preferably includes the curable resin layer containing a carboxylic acid anhydride from the viewpoint of forming an electrode protective film for a capacitance-type input device having excellent wet heat resistance.
  • the refractive index of the transparent film is 1.6 to 1.78, and preferably 1.65 to 1.74.
  • the transparent film may have a single layer structure or a laminated structure of two or more layers.
  • the refractive index of the transparent film means the refractive index of all layers.
  • the material of the transparent film is not particularly limited.
  • the preferable range of the material of the transparent film and the preferable range of physical properties such as the refractive index are the same as those of the above-described second resin layer.
  • the transparent film and the second resin layer are preferably made 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), or 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 resin used for the second resin layer in the transfer film. And other additives can be preferably used.
  • the transparent film may be an inorganic film. Examples of the material used for the inorganic film include the materials used for the second resin layer described above.
  • the refractive index of the third transparent film is preferably 1.5 to 1.55 from the viewpoint of improving the concealability of the transparent electrode pattern by approaching the refractive index of the transparent substrate described above. 52 is more preferable.
  • the method for producing the laminate of the present invention is not limited and can be produced by a known method.
  • the laminate of the present invention is preferably produced by a production method including a step of laminating the second resin layer and the curable resin layer of the transfer film described above on the transparent electrode pattern in this order.
  • the second resin layer and the curable resin layer of the laminate 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 2nd resin layer in the manufacturing method of a laminated body is formed into a film on a transparent electrode pattern and a transparent film of a non-pattern area directly or via another layer.
  • a non-contact surface (a transparent substrate constituting a capacitive input device) of a substrate (preferably a transparent substrate (front plate)) in advance.
  • the surface treatment can be performed on the surface on the opposite side to the surface on which the input means such as a finger is brought into contact.
  • a surface treatment silane coupling treatment
  • silane coupling agent those having a functional group that interacts with the photosensitive resin are preferable.
  • a liquid containing a silane coupling agent (0.3 mass% aqueous solution of N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) is sprayed for 20 seconds with a shower, Subsequently, it can be shower washed with pure water. 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 a laminator.
  • the transparent electrode pattern is obtained by using a 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 capacitance type input device described later.
  • the method of forming the curable resin layer includes a protective film removing step of removing the protective film from the transfer film, a transfer step of transferring the curable resin layer of the transfer film from which the protective film has been removed onto the transparent electrode pattern, and transparent
  • transferred on the electrode pattern, and the image development process which develops the exposed curable resin layer is mentioned.
  • the transfer film has the second resin layer, it is preferable that the curable resin layer and the second resin layer are simultaneously transferred, exposed and developed in the transfer step, the exposure step and the development step.
  • the transfer step is a step of transferring the curable resin layer (preferably the curable resin layer and the second resin layer) of the transfer film from which the protective film has been removed onto the transparent electrode pattern.
  • a method including a step of removing the temporary support after laminating the curable resin layer (preferably the curable resin layer and the second resin layer) of the transfer film on the transparent electrode pattern is preferable.
  • Transfer (lamination, bonding) of the curable resin layer (preferably the curable resin layer and the second resin layer) to the surface of the transparent electrode pattern is performed using a curable resin layer (preferably the curable resin layer and the second resin layer). Layer) on the surface of the transparent electrode pattern, and pressurizing and heating.
  • known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
  • the exposure step is a step of exposing the curable resin layer (preferably the curable resin layer and the second resin layer) transferred onto the transparent electrode pattern.
  • a predetermined mask is disposed above the curable resin layer (preferably the curable resin layer and the second resin layer) formed on the transparent electrode pattern and the temporary support, and then the light source above the mask. (Via a mask and a temporary support), and a method of exposing the curable resin layer (preferably the curable resin layer and the second resin layer).
  • a light source for exposure any light source capable of irradiating light (for example, 365 nm, 405 nm, etc.) in a wavelength region capable of curing the curable resin layer (preferably the curable resin layer and the second resin layer).
  • the exposure dose is usually about 5 to 200 mJ / cm 2 , preferably about 10 to 100 mJ / cm 2 .
  • the development step is a step of developing the exposed curable resin layer (preferably the curable resin layer and the second resin layer).
  • the development step means a development step of pattern-developing the pattern-exposed curable resin layer (preferably the curable resin layer and the second resin layer) with 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. For example, pKa (The negative logic of the acid dissociation constant); A developer containing 0.05 to 5 mol / L is preferred.
  • the developer when the curable resin layer (preferably the curable resin layer and the second resin layer) itself does not form a pattern is preferably a developer that does not dissolve the non-alkali development type colored composition layer.
  • a developer containing a compound of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferred.
  • 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 in the developer 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 may be any of paddle development, shower development, shower & spin development, dip development, and the like.
  • shower development an uncured part can be removed by spraying a developer onto the curable resin layer and the second resin layer after exposure.
  • 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.
  • 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 manufacturing method of the capacitive input device may have other processes such as a post exposure process and a post bake process.
  • a post exposure process When the curable resin layer (preferably the curable resin layer and the second resin layer) is thermosetting, it is preferable to perform a post-bake process.
  • patterning exposure and whole surface exposure may be performed after peeling the temporary support, or may be performed before peeling the temporary support, 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 manufacturing method of a laminated body includes the process of heat-processing the curable resin layer after transfer. It is more preferable to include a step of heat-treating the curable resin layer after transfer to make at least a part of the carboxyl group-containing acrylic resin a carboxylic acid anhydride.
  • the heat treatment of the curable resin layer after transfer is preferably after exposure and development, that is, a post-baking step after exposure and development.
  • the curable resin layer and the second resin layer are thermosetting, it is particularly preferable to perform a post-bake process.
  • it is preferable to perform 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 curable resin layer after the transfer so that at least a part of the carboxyl group-containing acrylic resin is a carboxylic acid anhydride is 100 to 160 ° C.
  • a film substrate is used as the substrate. In some cases, 140 to 150 ° C. is more preferable.
  • the laminate When the laminate further has a transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm on the side opposite to the side where the second resin layer of the transparent electrode pattern is formed, Is preferably formed directly on the transparent electrode pattern or via another layer such as a third transparent film.
  • the method for forming the transparent film is not particularly limited, but it is preferable to form the film by transfer or sputtering.
  • the laminate is preferably formed by transferring the transparent film-forming curable resin layer formed on the temporary support onto the transparent substrate, and is cured after transfer. More preferably, the film is formed.
  • the transparent film is an inorganic film
  • it is preferably formed by sputtering.
  • sputtering method methods described 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 a transparent substrate.
  • the method for producing a laminate preferably includes a step of simultaneously curing the curable resin layer and the second resin layer, and more preferably includes a step of pattern curing at the same time.
  • the transfer film it is preferable to laminate the second resin layer without curing the curable resin layer after laminating the curable resin layer.
  • the curable resin layer and the second resin layer transferred from the transfer film thus obtained can be simultaneously cured. Thereby, after transferring the curable resin layer and the second resin layer from the transfer film onto the transparent electrode pattern, it can be developed into a desired pattern by photolithography.
  • the method for producing a laminate includes an uncured portion of the curable resin layer and the second resin layer after the step of simultaneously curing the curable resin layer and the second 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 capacitive input device of the present invention includes the electrode protective film of the capacitive input device of the present invention or the laminate of the present invention.
  • a curable resin layer of a transfer film is laminated on a transparent substrate including a transparent electrode pattern using a transfer film. More preferably, the second resin layer and the curable resin layer of the transfer film are laminated in this order on the transparent substrate including the transparent electrode pattern. More preferably, the second resin layer and the curable resin layer disposed adjacent to the second resin layer are transferred from the transfer film onto the transparent electrode pattern of the capacitive input device.
  • the curable resin layer and the second resin layer transferred from the transfer film are preferably cured simultaneously, and the curable resin layer and the second resin layer are simultaneously pattern cured. Is more preferable.
  • the capacitive input device is developed by removing the uncured portions of the curable resin layer and the second resin layer that are transferred from the transfer film and simultaneously pattern-cured.
  • Capacitance type input device is not covered with curable resin layer (and second resin layer) because it is necessary to connect with flexible wiring formed on polyimide film at the end of routing wiring Is preferred.
  • This aspect is shown in FIG. FIG. 13 shows a capacitive input device including a lead wire (another conductive element 6) of a transparent electrode pattern and a terminal portion 31 of the lead wire.
  • the curable resin layer on the terminal portion 31 of the lead wiring is an uncured portion (unexposed portion), it is removed by development and the terminal portion 31 of the lead wiring is provided. Is exposed. Specific exposure and development modes are shown in FIGS. FIG.
  • FIG. 14 shows a state before the transfer film 30 having the curable resin layer and the second resin layer is laminated on the transparent electrode pattern of the capacitive input device and cured by exposure or the like.
  • photolithography that is, when cured by exposure, the curable resin layer having the shape shown in FIG. 9 and the cured portion (exposed portion) 33 of the second resin layer are subjected to pattern exposure and non-exposure using a mask. It can be obtained by developing the exposed area. Specifically, in FIG.
  • the opening 34 corresponding to the terminal portion of the routing wiring as the uncured portion of the curable resin layer and the second resin layer, and the outside of the outline of the frame portion of the capacitive input device The end of the transfer film having the curable resin layer and the second resin layer that protruded is removed, and the curable resin layer and the second curable resin layer for covering the terminal portion (extracted wiring portion) of the routing wiring are not covered. A cured portion (desired pattern) of the resin layer is obtained. Thereby, the flexible wiring produced on the polyimide film can be directly connected to the terminal portion 31 of the routing wiring, and the sensor signal can be sent to the electric circuit.
  • the capacitive input device includes a transparent electrode pattern, a second resin layer disposed adjacent to the transparent electrode pattern, and a curable resin layer disposed adjacent to the second resin layer. It is preferable to have a laminate in which the refractive index of the second resin layer is higher than the refractive index of the curable resin layer and the refractive index of the second resin layer is 1.6 or more.
  • the detail of the preferable aspect of the electrostatic capacitance type input device of this invention is demonstrated.
  • the capacitance type input device includes at least the following (3) to (5), (7) and (8) on the front plate (corresponding to the transparent substrate in the laminate) and the non-contact surface side of the front plate. It has an element and it is preferable to have the laminated body of this invention.
  • the second resin layer preferably corresponds to the second resin layer of the laminate of the present invention.
  • (8) curable resin layer is equivalent to the curable resin layer of the laminated body of this invention.
  • the curable resin layer is preferably a so-called transparent protective layer in a generally known capacitance type input device.
  • the second electrode pattern may or may not be a transparent electrode pattern, but is preferably a transparent electrode pattern.
  • the capacitive input device further includes (6) a first transparent electrode pattern and a second electrode pattern that are electrically connected to at least one of the first transparent electrode pattern and the second electrode pattern. It may have another conductive element.
  • the first transparent electrode pattern is in the laminate of the present invention. It preferably corresponds to a transparent electrode pattern.
  • the second electrode pattern is a transparent electrode pattern and (6) does not have another conductive element, (3) of the first transparent electrode pattern and (4) of the second electrode pattern It is preferable that at least one corresponds to the transparent electrode pattern in the laminate of the present invention.
  • the second electrode pattern is not a transparent electrode pattern and has (6) another conductive element, at least one of (3) the first transparent electrode pattern and (6) another conductive element It is preferable that this corresponds to the transparent electrode pattern in the laminate of the present invention.
  • the second electrode pattern is a transparent electrode pattern and (6) has another conductive element, (3) the first transparent electrode pattern, (4) the second electrode pattern, and (6) It is preferable that at least one of the other conductive elements corresponds to the transparent electrode pattern in the laminate of the present invention.
  • the capacitive input device further includes (2) a transparent film, (3) between the first transparent electrode pattern and the front plate, (4) between the second electrode pattern and the front plate, or (6) another conductivity.
  • a transparent film Preferably between the element and the front plate.
  • the 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, further improving the concealability of the transparent electrode pattern. It is preferable from the viewpoint.
  • the capacitance-type input device further has (1) a mask layer and / or a decoration layer as necessary.
  • the mask layer is provided as a black frame around the area touched by a finger or a touch pen so that the transparent wiring of the transparent electrode pattern cannot be visually recognized from the contact side or decorated.
  • a decoration layer is provided for decoration as a frame around the area
  • the mask layer and / or the decorative layer is (2) between the transparent film and the front plate, (3) between the first transparent electrode pattern and the front plate, (4) between the second transparent electrode pattern and the front plate, or (6) It is preferable to have between another electroconductive element and a front plate.
  • the mask layer and / or the decorative layer is more preferably provided adjacent to the front plate.
  • the capacitance-type input device is disposed adjacent to the second resin layer and the second resin layer disposed adjacent to the transparent electrode pattern.
  • 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 second resin layer. The problem of electrode pattern concealment can be improved.
  • FIG. 1A is a cross-sectional view illustrating a preferred configuration of a capacitive input device.
  • a capacitive input device 10 includes a transparent substrate (front plate) 1, a mask layer 2, and a transparent film 11 (preferably having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm).
  • a first transparent electrode pattern shown is a connection portion 3b of the first transparent electrode pattern
  • a second transparent electrode pattern 4 an insulating layer 5 another conductive element 6,
  • the aspect comprised from the 2nd resin layer 12 and the curable 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 capacitance type input device.
  • the capacitive input device 10 includes a transparent substrate (front plate) 1 and a transparent film 11 (preferably having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm).
  • the aspect comprised from the transparent electrode pattern 3, the 2nd transparent electrode pattern 4, the 2nd resin layer 12, and the curable resin layer 7 is shown.
  • the materials mentioned as the material for the transparent electrode pattern in the laminate can be used.
  • the side in which each element of the transparent substrate 1 which is a front plate is provided is called a non-contact surface side.
  • input is performed by bringing a finger or the like into contact with the contact surface (the surface opposite to the non-contact surface) of the transparent substrate 1 that is the front plate.
  • a mask layer 2 is provided on the non-contact surface of the transparent substrate 1 that is the front plate.
  • the mask layer 2 is a frame-shaped pattern around the display area formed on the non-contact surface side of the front panel of the touch panel, and is formed so as not to show the lead wiring and the like.
  • the capacitance type input device 10 is provided with a mask layer 2 so as to cover a part of the transparent substrate 1 as a front plate (a region other than the input surface in FIG. 2). ing.
  • the transparent substrate 1 as the front plate 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 with a plurality of pad portions extending in the first direction via the connection portions, and the first
  • a plurality of second transparent electrode patterns 4 comprising a plurality of pad portions that are electrically insulated from the transparent electrode pattern 3 and extend in a direction intersecting the first direction; and a first transparent electrode pattern 3 and an insulating layer 5 that electrically insulates the second transparent electrode pattern 4 are formed.
  • the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 may be the ITO film that can be used as the material of the transparent electrode pattern in the laminate. Is preferred.
  • the first transparent electrode pattern 3 and the second transparent electrode pattern 4 is opposite to the non-contact surface of the transparent substrate 1 that is the front plate and the transparent substrate 1 that is the front plate of the mask layer 2. It can be installed across both areas of the surface.
  • the second transparent electrode pattern 4 extends over both regions of the non-contact surface of the transparent substrate 1 that is the front plate and the surface opposite to the transparent substrate 1 that is the front plate of the mask layer 2. The installed mode is shown.
  • a vacuum laminator or the like can be obtained by using a photosensitive film having a specific layer configuration described later. Even without using expensive equipment, it is possible to perform lamination without generating bubbles at the mask portion boundary 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.
  • 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 may be integrally formed, or only the connection portion 3b is formed, and the pad portion 3a and the second transparent electrode pattern 3 are formed.
  • the 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 part 3b and a part of the pad part 3a are connected, and an insulating layer is formed. 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, the 2nd transparent electrode pattern 4, and the another electroconductive element 6 mentioned later in FIG. 3 is equivalent to the non-pattern area
  • FIG. 1A another conductive element 6 is installed on the surface side opposite to the transparent substrate 1 which is the front plate of the mask layer 2. 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 curable resin layer 7 is provided so as to cover all the components.
  • the curable resin layer 7 may be configured to cover only a part of each component.
  • the insulating layer 5 and the curable resin layer 7 may be the same material or different materials.
  • As a material which comprises the insulating layer 5, what was mentioned as a material of the curable resin layer in the laminated body or the 2nd resin layer can be used preferably.
  • FIG. 4 is a top view showing an example of the transparent substrate 1 in which the opening 8 is formed.
  • FIG. 5 is a top view showing an example of the front plate on which the mask layer 2 is formed.
  • FIG. 6 is a top view showing an example of the front plate on which the first transparent electrode pattern 3 is formed.
  • FIG. 7 is a top view showing an example of a front plate 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 front plate on which conductive elements 6 different from the first and second transparent electrode patterns are formed.
  • a transfer film is placed on the surface of the transparent substrate 1 which is a front plate on which each element is arbitrarily formed. It can be formed by transferring the second resin layer and the curable resin layer.
  • the mask layer 2 In the manufacturing method of the capacitance type input device, at least one element of the mask layer 2, the first transparent electrode pattern 3, the second transparent electrode pattern 4, the insulating layer 5, and another conductive element 6.
  • the photosensitive film which has a temporary base material and a photocurable resin layer in this order.
  • the resist component does not leak or protrude from the edge of the transparent substrate, so that the non-contact surface of the transparent substrate is not contaminated.
  • a simple process it is possible to manufacture a touch panel that is thin and lightweight.
  • the photosensitive film may be subjected to pattern exposure as necessary after being laminated on a transparent substrate or the like.
  • the photosensitive film may be a negative type material or a positive type material.
  • a pattern can be obtained by developing and removing the unexposed portion and when the photosensitive film is a positive material.
  • the 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.
  • Photosensitive film A photosensitive film other than the transfer film of the present invention, which is preferably used when manufacturing a capacitance-type input device, is described in paragraphs 0222 to 0255 of JP-A No. 2014-178922. Incorporated herein.
  • An electrostatic capacitance type input device and an image display device including the electrostatic capacitance type input device as components are “latest touch panel technology” (Techno Times, issued on July 6, 2009), supervised by Yuji Mitani, The configurations disclosed in “Technology and Development of Touch Panel”, CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, and the like can be applied.
  • Example 1 ⁇ Production of transfer film> (Formation of curable resin layer) Using a slit nozzle on a 75 ⁇ m thick polyethylene terephthalate film (temporary support), adjust the coating liquid for the curable resin layer having the following formulation 101 so that the thickness after drying is 10 ⁇ m. Applied. This applied layer was dried at 100 ° C. for 2 minutes, and then dried at 120 ° C. for 1 minute to form a curable resin layer.
  • the 2nd coating liquid for resin layers which consists of the following prescription 201 was adjusted and applied so that the thickness after drying might be set to 100 nm on the curable resin layer.
  • the applied layer was dried at 80 ° C. for 1 minute, and then dried at 110 ° C. for 1 minute to form a second resin layer disposed in direct contact with the curable resin layer.
  • the formulation 201 was prepared using a resin having an acid group and an aqueous ammonia solution. By mixing these, the acid group-containing resin is neutralized with an aqueous ammonia solution to prepare a second resin layer coating solution that is an aqueous resin composition containing an ammonium salt of the acid group-containing resin.
  • particle ZrO 2 particles (Nanouse OZ-S30M, manufactured by Nissan Chemical Industries, Ltd., solid content 30.5%, methanol 69.5%, refractive index 2.2, average particle diameter of about 12 nm ZrO 2 particles) ⁇ 4.28 parts
  • the transfer film of Example 1 was wound into a roll shape so that the protective film was on the outside, and a roll was formed. It was stored in a roll state at 40 ° C. and a relative humidity of 80% for 7 days. In the transfer film evaluation described below, a transfer film unwound from a roll was used.
  • Example 2 In Example 1, the transfer film of Example 2 was produced like Example 1 except having replaced protective film A1 with protective film A2 shown below.
  • Example 3 In Example 1, the transfer film of Example 3 was produced like Example 1 except having replaced protective film A1 with protective film A3 shown below.
  • Example 1 transfer films of Examples 4 to 14 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that the protective film A1 was replaced with the protective films A4 to A17 shown in Table 2 below. .
  • the characteristics of the protective films A4 to A17 are shown below.
  • the protective film A4 is a PET film.
  • the protective film A5 is a polyvinyl chloride film.
  • the protective film A6 is a polycarbonate film.
  • the protective film A7 is a highly oriented PET film.
  • the protective film A8 is a low density polyethylene film.
  • the protective film A9 is a smooth PET film.
  • the protective film A10 is a polypropylene film.
  • the protective film A11 is an ultra-smooth PET film.
  • the protective film A12 is a roughened polypropylene film.
  • the protective film A13 is a 12 ⁇ m-thick polypropylene film.
  • the protective film A14 is a 15 ⁇ m-thick polypropylene film.
  • the protective film A15 is a 20 ⁇ m thick polypropylene film.
  • the protective film A16 is a 70 ⁇ m thick polypropylene film.
  • the protective film A17 is an 80 ⁇ m thick polypropylene film.
  • Example 15 to 19 The transfer of Examples 15 to 19 was carried out in the same manner as in Example 1 except that the ZrO 2 particles added to the second coating solution for the resin layer were replaced with the contents shown in the following table. A film was prepared.
  • Double bond consumption rate of curable resin layer When the curable resin layer was applied and dried on the temporary support, a section of the curable resin layer was cut from the surface using a microtome. 2 mg of KBr powder was added to 0.1 mg of this slice and mixed well under a yellow light. This mixture was used as a measurement sample of a UV (ultraviolet) uncured product of the curable resin layer in the measurement of the double bond consumption rate.
  • FT-IR is a Fourier Transform Infrared Spectroscopy (Fourier Transform Infrared Spectroscopy). Coating and drying a curable peak intensity of UV uncured product of the resin layer (double bond remaining amount) A 1 of immediately after the peak of the film sections of the cured resin layer in the transfer films of Examples and Comparative Examples The strength B 1 was determined.
  • the double bond consumption rate of the curable resin layer was calculated according to the following formula.
  • Double bond consumption rate of curable resin layer ⁇ 1- (B 1 / A 1 ) ⁇ ⁇ 100%
  • the curable resin layer was not exposed after the curable resin layer was applied and dried on the temporary support.
  • reference The peak intensity C 1 of the film section of the curable resin layer in the example transfer film is obtained. Then, the double bond consumption rate of the curable resin layer in the transfer film of the reference example is calculated according to the following formula.
  • Double bond consumption rate of curable resin layer in transfer film of Reference Example ⁇ 1- (C 1 / A 1 ) ⁇ ⁇ 100%
  • the peak intensity A 1 of the UV uncured product of the curable resin layer may be obtained by separately preparing a UV uncured product sample of the curable resin layer for A 1 measurement. Specifically, the composition of the curable resin layer of the transfer film is analyzed and specified, a UV uncured product sample of the curable resin layer for A 1 measurement is prepared, and A 1 can be obtained from this sample. .
  • Double bond consumption rate of the second resin layer When the second resin layer is applied and dried on the curable resin layer, a section of the second resin layer is cut from the surface using a microtome. did. 2 mg of KBr powder was added to 0.1 mg of this slice and mixed well under a yellow light. This mixture was used as a measurement sample of the UV uncured product of the second resin layer in the measurement of the double bond consumption rate.
  • the double bond consumption rate of the 2nd resin layer in the transfer film of a reference example is calculated according to a following formula.
  • Consumption rate of double bond of second resin layer in transfer film of reference example ⁇ 1- (C 2 / A 2 ) ⁇ ⁇ 100%
  • the peak intensity A 2 of the UV uncured product of the second resin layer may be obtained separately by separately preparing a UV uncured product sample of the curable resin layer for A 2 measurement. Specifically, the composition of the second resin layer of the transfer film is analyzed and specified, a UV uncured product sample of the second resin layer for A 2 measurement is prepared, and A 2 is obtained from this sample. Can do.
  • the refractive index n 1 and thickness T 1 of the curable resin layer and the refractive index n 2 and thickness T 2 of the second resin layer were measured using a reflection spectral film thickness meter FE-3000 (manufactured by Otsuka Electronics Co., Ltd.). And determined as follows. (1) The temporary support used in each example and comparative example was cut into a length of 5 cm ⁇ 5 cm on both sides.
  • PT100 NB Lintec Co., Ltd.
  • OCT polyethylene terephthalate
  • the laminate was made by bonding (manufactured).
  • the reflection spectrum (wavelength: 430 to 800 nm) of the laminate of the temporary support and black PET was evaluated using a reflection spectral film thickness meter FE-3000, and the refractive index n 0 of the temporary support at each wavelength was determined.
  • the laminated body which made the black PET material contact the temporary support body surface of these samples through the transparent adhesive tape (OCA tape 8171CL, 3M Co., Ltd. product) was produced.
  • TEM Transmission Electron Microscope, HT7700, Hitachi High-Tech Fielding Co., Ltd.
  • TEM Transmission Electron Microscope
  • HT7700 Hitachi High-Tech Fielding Co., Ltd.
  • the thickness of the curable resin layer was measured at 10 points to determine the average value, and the first expected value T 1 (I) of the average value of the thickness of the curable resin layer was determined.
  • T 1 (I) the first expected value of the average value of the thickness of the curable resin layer was determined.
  • a reflection spectral film thickness meter FE-3000 manufactured by Otsuka Electronics Co., Ltd.
  • the reflection spectrum (wavelength: 430 to 800 nm) of a laminate of a curable resin layer, a temporary support and black PET was evaluated, and curing at each wavelength was performed.
  • the second expected value T 1 (II) of the refractive index n 1 of the curable resin layer and the average value of the thickness of the curable resin layer was determined, and the refractive index n 1 of the curable resin layer at a wavelength of 550 nm is shown in Table 2 below. did.
  • the value of the refractive index n 0 of the temporary support obtained in the above (1) and the average value of the average thickness of the curable resin layer The expected value T 1 (I) of 1 is input to the thickness calculation software attached to the FE 3000, and then the refractive index n 1 of the curable resin layer is calculated from the reflection spectrum of the laminate of the curable resin layer, the temporary support, and the black PET.
  • the second expected value T 1 (II) of the average value of the thickness of the curable resin layer was obtained by fitting by simulation calculation.
  • the second resin layer, the curable resin layer, the temporary support From the reflection spectrum of the black PET laminate, the refractive index n 2 of the second resin layer and the thicknesses of the curable resin layer and the second resin layer at 1000 measurement points were obtained by fitting by simulation calculation. Furthermore, the average value of the thickness of the curable resin layer and the second resin layer was calculated to obtain n 1 , n 2 , T 1 , and T 2 .
  • the fitting value of the simulation can be improved by inputting the expected value obtained by conducting the structural analysis with TEM to the reflection spectral film thickness meter.
  • the protective film of the obtained transfer film was peeled off.
  • the surface of the peeled protective film was visually observed under the illumination of a fluorescent lamp, and was transferred from the layer (second resin layer or curable resin layer) in contact with the protective film to the surface of the protective film with a diameter of 100 ⁇ m or more.
  • Transcripts were extracted.
  • the area of 1 m 2 of the protective film was observed three times, and the average number of transferred products per 1 m 2 of the protective film was calculated.
  • the number of transferred products per 1 m 2 of the surface of the protective film was defined as the number of transfer defects per 1 m 2 of the transfer film.
  • the number of transfer defects in 1 m 2 per transfer film was scored by the following criteria.
  • ⁇ Dent> Number of dent defects
  • the protective film of the obtained transfer film was peeled off.
  • the transfer film after peeling off the protective film was visually observed under illumination of a fluorescent lamp, and a dent having a diameter of 100 ⁇ m or more was extracted.
  • the area of 1 m 2 of the transfer film was observed three times, and the number of dent defects per 1 m 2 of the transfer film was calculated on average.
  • the number of dent defects per 1 m 2 of the transfer film was scored according to the following criteria.
  • the simple evaluation of the dent is preferably 15 sheets or less, more preferably 10 sheets or less, and further preferably 5 sheets or less.
  • the material of the material-C shown in Table 1 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.
  • Transparent film substrate temperature 150 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa an ITO thin film having a thickness of 40 nm and a refractive index of 1.82 was formed, and the transparent film and the transparent electrode were formed on the transparent film substrate.
  • a layered film was obtained.
  • the surface resistance of the ITO thin film was 80 ⁇ / ⁇ ( ⁇ per square). DC is direct current.
  • a coating solution for a thermoplastic resin layer having the following formulation H1 was applied using a slit nozzle and dried.
  • an intermediate layer coating solution having the following formulation P1 was applied and dried.
  • a coating liquid for photocurable resin layer for etching comprising the following formulation E1 was applied and dried.
  • a laminate comprising a thermoplastic resin layer having a dry thickness of 15.1 ⁇ m, an intermediate layer having a dry thickness of 1.6 ⁇ m, and a photocurable resin layer for etching having a thickness of 2.0 ⁇ m is formed on the temporary base material.
  • a protective film (thickness 12 ⁇ m polypropylene film) was pressure-bonded.
  • a photosensitive film E1 for etching which is a transfer material in which the temporary base material, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the etching photocurable resin layer are 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 60,000, acid value 163 mg KOH / g) ... 16.0 parts by mass 1 (Brand name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.) ... 5.6 parts by mass, 0.5-methylene tetraethylene oxide monomethacrylate adduct of hexamethylene diisocyanate ...
  • 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 the photocurable resin layer for etching is set to 200 ⁇ m, and the photocurable resin for etching is interposed through the thermoplastic resin layer and the intermediate layer.
  • the layer was pattern-exposed with an exposure dose of 50 mJ / cm 2 (i-line).
  • 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.), Treated for 100 seconds.
  • ITO etchant hydrochloric 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 It was immersed in a resist stripping tank containing a product manufactured by Products Co., Ltd. (liquid temperature: 45 ° C.) and treated for 200 seconds, whereby the photocurable resin layer for etching was removed by this stripping treatment, and a transparent film and a transparent film on the transparent film substrate A transparent electrode pattern film in which a transparent electrode pattern was formed was obtained.
  • a resist stripping solution N-methyl-2-pyrrolidone, monoethanolamine, a surfactant (trade name: Surfynol 465, air It was immersed in a resist stripping tank containing a product manufactured by Products Co., Ltd. (liquid temperature: 45 ° C.) and treated for 200 seconds, whereby the photocurable resin layer for etching was removed by this
  • the transfer was performed at a transparent film substrate temperature of 40 ° C., a rubber roller temperature of 110 ° C., a linear pressure of 3 N / cm, and a conveyance speed of 2 m / min.
  • the curable resin layer covered the transparent film and the transparent electrode pattern of the transparent electrode pattern film in which the transparent film and the transparent electrode pattern were formed on the transparent film substrate.
  • the curable resin layer of the transfer film of Example 19 and the temporary support were transferred in this order onto the transparent electrode pattern film to obtain a laminate before exposure.
  • the exposure mask (quartz exposure mask with overcoat formation pattern) surface
  • the distance between the substrate and the temporary support was set to 125 ⁇ m, and pattern exposure was performed through the temporary support with an exposure amount of 100 mJ / cm 2 (i-line).
  • the laminate transparent film substrate
  • the laminate after pattern exposure was washed for 60 seconds at 32 ° C. with a 2% aqueous solution of sodium carbonate. Residues were removed by spraying ultrapure water from the ultra-high pressure cleaning nozzle onto the transparent film substrate after the cleaning treatment.
  • Example 19 having a transparent film, a transparent electrode pattern, and a curable resin layer disposed in direct contact with the transparent electrode pattern in this order on the transparent film substrate. A laminate was obtained. From the above steps, it was confirmed that the transfer film of the present invention has photolithographic properties.
  • the transfer film of the present invention has photolithographic properties, generates less bubbles, and has few transfer defects.
  • the transfer film of Comparative Example 1 in which the oxygen permeation coefficient of the protective film was lower than the lower limit defined in the present invention had many bubbles.
  • the transfer film of Comparative Example 2 in which the surface roughness of the protective film was lower than the lower limit specified in the present invention had many transfer defects.
  • the transfer film of Comparative Example 3 in which the surface roughness of the protective film exceeded the upper limit defined in the present invention many bubbles were generated.
  • N 1, n 2, T 1 and T 2 in the laminate of the Examples and Comparative Examples were respectively n 1, n 2, T 1 and T 2 coincide in the transfer films of Examples and Comparative Examples.
  • N 1 , n 2 , T 1, and T 2 in the obtained laminate were measured by using a reflection spectral film thickness meter FE-3000 (manufactured by Otsuka Electronics Co., Ltd.), and n 1 in the transfer films of each Example and Comparative Example.
  • N 2 , T 1 and T 2 were obtained by repeating the same method for each layer. The outline is shown below.
  • the sample piece which contacted the black PET material was produced through the tape (OCA tape 8171CL, 3M Co., Ltd. product).
  • the sample piece was subjected to structural analysis using a transmission electron microscope (TEM), and the expected value of the thickness of each layer was determined.
  • TEM transmission electron microscope
  • the sample spectrum was measured at 100 measurement points on a straight line in an arbitrary direction at 0.2 mm intervals at a measurement spot with a diameter of 40 ⁇ m. evaluated.
  • the second resin layer, the transparent film substrate, the transparent film, and the transparent electrode pattern Transparent film substrate / transparent film / transparent electrode pattern with the expected value of the average value of the refractive index and the thickness of the curable resin layer and the expected value of the average value of the thickness of the second resin layer substituted in the calculation formula curable in / the second resin layer / cured resin layer 5 layer component measurement point of the refractive index n 2 and 100 points of refractive index n 1 and the second resin layer of the cured resin layer from the reflection spectra of the The thicknesses of the resin layer and the second resin layer were obtained by fitting by simulation calculation.
  • n 1 , n 2 , T 1, and T 2 were calculated.
  • an arbitrary direction is defined as a direction parallel to one side of the sample piece, and 100 measurement points (that is, 2 cm long) are equally set to a range of 1 cm from the center of one side of the sample piece.
  • WR D * VR / (1.1 * (1-VR) + D * VR)
  • D Specific gravity of metal oxide particles
  • the content of the metal oxide particles in the curable resin layer or the second resin layer of the laminates of the examples and comparative examples can also be calculated from the composition of the curable resin layer or the second resin layer. .
  • the transfer film of the present invention can be preferably used as a material for a touch panel (particularly a capacitive input device) or an image display device provided with a touch panel (particularly a capacitive input device) as a constituent element. . Since the transfer film of the present invention has photolithographic properties, a desired pattern can be formed with higher production efficiency than the cutting method.

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JP6687794B2 (ja) * 2019-09-02 2020-04-28 富士フイルム株式会社 転写フィルム、静電容量型入力装置の電極保護膜、積層体および静電容量型入力装置
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