JP5926128B2 - Manufacturing method of laminated body having photocurable resin layer, capacitive input device, manufacturing method thereof, and image display device including the same - Google Patents

Description

  The present invention relates to a method for producing a laminate having a photocurable resin layer, a method for producing a capacitive input device capable of detecting a contact position of a finger as a change in capacitance, and a static obtained by the production method. The present invention relates to a capacitive input device and an image display device including the capacitive input device as a constituent element.

  In recent years, electronic devices such as mobile phones, car navigation systems, personal computers, ticket vending machines, and bank terminals have been equipped with a tablet-type input device on the surface of a liquid crystal device, etc., and an instruction image displayed in the image display area of the liquid crystal device In some cases, information corresponding to the instruction image can be input by touching a part where the instruction image is displayed with a finger or a touch pen.

  Such input devices (touch panels) include a resistance film type and a capacitance type. However, the resistance film type input device has a drawback that it has a narrow operating temperature range and is susceptible to changes over time because it has a two-layer structure of film and glass that is shorted by pressing the film.

  On the other hand, the capacitance-type input device has an advantage that a light-transmitting conductive film is simply formed on a single substrate. In such a capacitance-type input device, for example, electrode patterns are extended in directions intersecting each other, and when a finger or the like comes into contact, the capacitance between the electrodes is detected to detect the input position. (For example, refer to Patent Document 1 below).

  In addition, as an electrostatic capacitance type input device, an alternating current of the same phase and the same potential is applied to both ends of the translucent conductive film to detect a weak current flowing when a capacitor is formed in contact with or close to a finger. Some types detect the input position. As such a capacitive input device, a plurality of first transparent electrode patterns and a plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connecting portions. And a plurality of second transparent electrode patterns comprising a plurality of pad portions formed to extend in a direction crossing the first direction and electrically insulated via an interlayer insulating layer An input device is disclosed (for example, see Patent Document 2 below). However, since the capacitance type input device is formed by laminating a glass front plate on the produced capacitance type input device, the capacitance type input device described in Patent Document 2 is thick and heavy. .

  Furthermore, a capacitive touch panel is disclosed in which a mask layer, a sense circuit, and an interlayer insulating layer are integrally formed on the non-contact side surface of the front plate (see, for example, Patent Document 3 below). Patent Document 3 describes that the capacitive touch panel has a front plate integrated with the capacitive input device, so that a thin layer / lightweight can be achieved. Is not listed.

  On the other hand, ITO (Indium Tin Oxide) is used as the material for the first and second transparent electrodes. After vacuum deposition and patterning with liquid resist (exposure / development), the portions not covered with liquid resist are etched. And the method of forming a desired transparent electrode pattern is disclosed (for example, refer patent document 4). However, according to this method, there is a problem that the manufacturing apparatus is expensive and the cost reduction is not easy.

  On the other hand, from the viewpoint of forming a capacitive input device capable of realizing a thin layer / weight reduction, a single-wafer plastic substrate or a roll-shaped plastic film has been proposed as a flexible support other than glass. (For example, see Patent Document 5 below).

JP 2007-122326 A Japanese Patent No. 4506785 JP 2009-193587 A US Patent Application Publication No. 2008-0264699 JP-A-4-264613 JP 2006-307056 A JP 2004-272043 A JP 2008-242190 A JP 2011-095716 A

  However, when a photocurable resin layer is laminated on a flexible support by the method described in Patent Document 5, an improvement is required in the adhesion between the flexible support and the photocurable resin layer. It was. Moreover, the improvement was calculated | required also from a viewpoint of a defect when hardening | curing a photocurable resin layer.

  The problem to be solved by the present invention is to have a photocurable resin layer on a flexible support, have excellent adhesion between the flexible support and the photocurable resin layer after curing, and have a flexible support after curing. It is providing the manufacturing method of the laminated body which has a photocurable resin layer with few defects to the edge part of a body.

  Here, when forming a photocurable resin layer on a conventional glass support, surface treatment is performed with a silane coupling agent, or irregularities are formed on the support surface by plasma treatment or ultraviolet treatment. It is known that the adhesion of the upper layer can be improved. However, as a result of studies by the present inventors, it has been found that these methods are not always effective for improving the adhesion between a flexible support such as a plastic substrate and a photocurable resin layer.

Here, in the display device field other than the capacitive input device, Patent Documents 6 and 7 describe a method of alkali saponifying a cellulose acylate film as a method for improving the surface of a flexible support. However, no investigation has been made on improving adhesion when laminated with a photocurable resin.
Patent Document 8 describes a color filter in which a plastic film is used in place of a conventional glass substrate and a light-shielding layer is formed using a liquid black resist. It was difficult to form a light shielding layer up to the part.
Patent Document 9 discloses a colored resin pattern for a color filter obtained by laminating a transfer material having a photosensitive resin layer containing a colored photosensitive resin composition on an alkali-free glass substrate, and then curing the pattern by exposing the pattern. However, an example in which a photosensitive resin layer was transferred onto a flexible support was not described. Further, when the present inventor examined, when a photocurable resin layer was formed on a flexible support using the photosensitive film described in Patent Document 9, a light shielding pattern was formed up to the end of the flexible support after curing. Although it was possible to form a photo-curable resin layer such as the above, it was found that adhesion was insufficient when patterning and peeling occurred.

  On the other hand, when the inventor transferred the photosensitive film transfer material provided with the photocurable resin layer after alkali-treating at least one surface of the flexible support, the flexibility after curing was determined. It has been found that the adhesion between the support and the photocurable resin layer is improved, and defects are reduced to the end of the flexible support after curing after curing.

The present invention which is a specific means for solving the above-mentioned problems is as follows.
[1] A photosensitive film comprising a step of alkali-treating at least one surface of a flexible support, and a photocurable resin layer on the temporary support on the alkali-treated surface of the flexible support. The method for producing a laminate having a photocurable resin layer, comprising the steps of: laminating and pressure-bonding the photocurable resin layer.
[2] In the method for producing a laminate having the photocurable resin layer according to [1], the photosensitive film includes at least the temporary support, the thermoplastic resin layer, and the photocurable resin layer in this order. It is preferable to have.
[3] In the method for producing a laminate having a photocurable resin layer according to [1] or [2], the photocurable resin layer preferably contains a carboxylic acid group-containing resin.
[4] In the method for producing a laminate having the photocurable resin layer according to any one of [1] to [3], the flexible support is a cellulose-based support or a polyester-based support. Preferably there is.
[5] The method for producing a laminate having the photocurable resin layer according to any one of [1] to [4] preferably performs the pressure-bonding step while heating.
[6] In the method for producing a laminate having the photocurable resin layer according to any one of [1] to [5], the photocurable resin layer is at least one of a black colorant and a white colorant. It is preferable to include one.
[7] A cured product obtained by exposing a laminate having a photocurable resin layer produced by the method for producing a laminate having the photocurable resin layer according to any one of [1] to [6]. A capacitance-type input device comprising a laminate.
[8] In the capacitive input device according to [7], it is preferable that the cured product laminate is patterned.
[9] The capacitive input device according to [7] or [8] preferably includes a mask layer, and at least one layer of the cured product laminate is the mask layer.
[10] The capacitance-type input device according to any one of [7] to [9] includes the following elements (1) to (5), and at least one layer of the cured product laminate is: The (1) mask layer is preferred.
(1) Mask layer (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (3) The first transparent electrode pattern and the electric A plurality of second transparent electrode patterns comprising a plurality of pad portions that are electrically insulated and extend in a direction intersecting the first direction (4) The first transparent electrode pattern and the second An insulating layer that electrically insulates the transparent electrode pattern (5) electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern, and the first transparent electrode pattern and the second transparent electrode pattern Photocurability manufactured with the manufacturing method of the laminated body which has a photocurable resin layer as described in any one of electroconductive element [11] [1]-[6] different from a 2nd transparent electrode pattern. A step of exposing a laminate having a resin layer; A method of manufacturing a capacitance-type input device comprising:
[12] In the method for manufacturing a capacitance-type input device according to [11], it is preferable to pattern-expose the laminate having the photocurable resin layer.
[13] The method for manufacturing a capacitance-type input device according to [11] or [12] is a method for manufacturing a capacitance-type input device having a mask layer, and the laminate having the photocurable resin layer. It is preferable to form the mask layer by exposing the mask.
[14] The method for manufacturing a capacitive input device according to any one of [11] to [13] is a method for manufacturing a capacitive input device having the following elements (1) to (5): It is preferable that the laminated body having the photocurable resin layer is exposed to form the (1) mask layer.
(1) Mask layer (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (3) The first transparent electrode pattern and the electric A plurality of second transparent electrode patterns comprising a plurality of pad portions that are electrically insulated and extend in a direction intersecting the first direction (4) The first transparent electrode pattern and the second An insulating layer that electrically insulates the transparent electrode pattern (5) electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern, and the first transparent electrode pattern and the second transparent electrode pattern The image display apparatus provided with the electrostatic capacitance type input device as described in any one of electroconductive element [15] [7]-[10] different from a 2nd transparent electrode pattern.

According to the present invention, a photocurable resin layer is provided on a flexible support, and the adhesive has excellent adhesion between the flexible support and the photocurable resin layer after curing. The manufacturing method of the laminated body which has a photocurable resin layer with few defects to a part can be provided.
Moreover, according to the manufacturing method of the capacitive input device of the present invention including the manufacturing method of the laminate having the photocurable resin layer of the present invention, the capacitive input device capable of being thinned / lightened is provided. Therefore, it can be manufactured with high quality by a simple process.

It is sectional drawing which shows an example of a structure of the electrostatic capacitance type input device of this invention. It is sectional drawing which shows another example of a structure of the electrostatic capacitance type input device of this invention. It is sectional drawing which shows another example of a structure of the electrostatic capacitance type input device of this invention. It is sectional drawing which shows another example of a structure of the electrostatic capacitance type input device of this invention. It is explanatory drawing which looked at an example of the electrostatic capacitance type input device of this invention from the mask layer side. It is explanatory drawing which shows an example of the 1st transparent electrode pattern in this invention, and a 2nd transparent electrode pattern. It is a top view which shows an example of the tempered glass in which the opening part was formed. It is a top view which shows an example of the front board in which the mask layer was formed. It is a top view which shows an example of the front plate in which the 1st transparent electrode pattern was formed. It is a top view which shows an example of the front plate in which the 1st and 2nd transparent electrode pattern was formed. It is a top view which shows an example of the front plate in which the electroconductive element different from the 1st and 2nd transparent electrode pattern was formed. It is explanatory drawing which shows a metal nanowire cross section. It is the schematic which shows the pattern of each mask used in the Example. It is the schematic which shows the structure of the mask A used in the Example. It is the schematic which shows the structure of the laminated body which has a photocurable resin layer obtained using the mask A. FIG. It is the schematic which shows the structure of the mask B used in the Example. It is the schematic which shows the structure of the laminated body which has a photocurable resin layer obtained using the mask B. FIG.

  Hereinafter, the manufacturing method of the laminated body which has the photocurable resin layer of this invention, the manufacturing method of an electrostatic capacitance type input device, an electrostatic capacitance type input device, and an image display apparatus are demonstrated.

[Method for producing a laminate having a photocurable resin layer]
The method for producing a laminate having the photocurable resin layer of the present invention (hereinafter also referred to as the production method of the present invention) comprises a step of alkali-treating at least one surface of a flexible support, and the flexible support. A step of superposing the photocurable resin layer of a photosensitive film having a photocurable resin layer on a temporary support on the surface of the body that has been subjected to alkali treatment, and press-bonding the layer.
With such a configuration, the production method of the present invention has a photocurable resin layer on the flexible support, and is excellent in adhesion between the flexible support and the photocurable resin layer after curing. A method for producing a laminate having a photocurable resin layer with few defects up to the end of the flexible support after curing can be provided.

<< Process for alkali treatment of at least one surface of flexible support >>
The production method of the present invention includes a step of subjecting at least one surface of the flexible support to an alkali treatment.
(Flexible support)
The flexible support used in the production method of the present invention will be described.
The flexible support in the present invention includes a cellulose-based support such as a triacetyl cellulose (TAC) resin film, a polyester-based support such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) -modified polyester, and polyethylene (PE). Resin films, polypropylene (PP) resin films, polystyrene resin films, polyolefin resin films such as cyclic olefin resins, vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin films, polysulfone (PSF) resin film, polyethersulfone (PES) resin film, polycarbonate (PC) resin film, polyamide resin film, polyimide resin film, acrylic resin film, etc. You can gel.
Among these, in terms of transparency, heat resistance, ease of handling, strength, and cost, it is preferably a cellulose-based support or a polyester-based support, and a biaxially stretched polyethylene terephthalate film or a biaxially stretched polyethylene naphthalate film. A triacetyl cellulose (TAC) resin film is more preferable.
The thickness of the flexible support is desirably 30 μm to 250 μm, more preferably 30 to 100 μm, and particularly preferably 30 to 90 μm.
The flexible support may have a single layer structure or a laminated structure of two or more layers. In the case of a laminated structure of two or more layers, the total thickness of all layers is preferably in the above range.

(Alkaline treatment conditions)
In the flexible support in the present invention, the photocurable resin layer of the photosensitive film having the photocurable resin layer on the temporary support is overlaid on the alkali-treated surface of the flexible support described later. Then, before the step of overlapping and pressure bonding, at least one surface of the flexible support is alkali-treated.
As the alkali treatment, any method such as a method of immersing a flexible support in an alkali solution or a method of spraying or applying an alkaline solution to the surface of the flexible support can be used. In the present invention, it is more preferable to perform alkali saponification by a coating method, in which only one surface of the flexible support can be uniformly saponified without unevenness, that is, saponification by a step of applying an alkaline solution to the flexible support. . On the other hand, in the saponification by the dipping method, in particular, in the alkali saponification containing an organic solvent, the treatment speed can be remarkably increased as compared with those not containing an organic solvent.

The saponification is preferably performed at a temperature at which deformation of the flexible support for saponification, alteration of the alkaline solution, or the like does not occur, or a processing temperature in a range not exceeding 120 ° C, more preferably 25 ° C to 120 ° C. Furthermore, it is preferable to carry out at a temperature of 25 ° C. or higher and 115 ° C. or lower.
Further, the saponification time is determined by appropriately adjusting the alkali solution and the temperature at the time of saponification, but it is preferably performed in the range of 1 second to 60 seconds, more preferably 1 to 20 seconds, and more preferably 5 to 15 It is particularly preferable to carry out a second.
Furthermore, the alkali saponification method of the present invention preferably includes a step of applying an alkaline solution to a flexible support having a temperature of room temperature (25 ° C.) or higher. Furthermore, it is preferable to have a step of maintaining the temperature of the flexible support at least at room temperature or higher in addition to these steps. The temperature at the time of saponification can be made into the said desired temperature, and is preferable.

Further, in the present invention, in order to bring the flexible support to a predetermined temperature, the flexible support is adjusted in advance to a predetermined temperature (temperature higher than room temperature) before applying the alkaline solution. It is preferable to have a process. It is also preferable to combine the step of adjusting the alkaline solution to a predetermined temperature in advance. In particular, it is preferable to have a step of heating to a predetermined temperature (a temperature equal to or higher than room temperature) before application. "The temperature of the flexible support is set to a predetermined temperature", "Flexible support whose temperature is room temperature or higher", and "The temperature of the flexible support is maintained at room temperature or higher" are flexible support. The entire temperature does not need to be a predetermined temperature, and the surface to be treated by saponification, that is, the surface of the flexible support on which the saponification reaction occurs may be a predetermined temperature.
Here, means for heating the flexible support to room temperature or higher include direct heating by hot air collision (blowing), contact heat transfer by a heating roll, induction heating by microwaves, or radiant heat heating by an infrared heater. Can be preferably used. In particular, contact heat transfer using a heating roll is preferable in that heat transfer efficiency is high and it can be performed with a small installation area, and that the flexible substrate temperature rises quickly at the start of conveyance. A general double jacket roll or electromagnetic induction roll (manufactured by Tokuden) can be used. The film surface temperature after heating is preferably 25 to 120 ° C, more preferably 25 to 100 ° C.

(Alkaline solution)
In the present invention, the alkaline solution used for the alkali treatment is preferably an alkaline solution having a pH of 11 or more. More preferably, the pH is 12-14. Examples of the alkaline agent used in the alkaline solution include inorganic alkaline agents such as sodium hydroxide, potassium hydroxide and lithium hydroxide, diethanolamine, triethanolamine, DBU (1,8-diazabicyclo [5,4,0]. -7-undecene), DBN (1,5-diazabicyclo [4,3,0] -5-nonene), tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethyl Organic alkali agents such as butylammonium hydroxide are also used. These alkaline agents can be used alone or in combination of two or more, and a part thereof may be added in the form of a salt, for example, halogenated.

  Among these alkali agents, alkali metal hydroxides are preferable. Particularly, use of sodium hydroxide or potassium hydroxide is preferable because pH adjustment in a wide region can be achieved by adjusting these amounts. The hydroxide ion concentration in the alkaline solution is determined according to the type of alkali agent used, the reaction temperature and the reaction time. The hydroxide ion concentration is preferably 0.1 to 5 mol / kg in the alkaline solution, and 3 to 3 mol / kg is more preferable. The solvent of the alkaline solution of the present invention is preferably a mixed solution of water and a water-soluble organic solvent. Any organic solvent that is miscible with water can be used as the organic solvent, but those having a boiling point of 120 ° C. or lower, more preferably 60 to 120 ° C., and particularly preferably 60 to 100 ° C. or lower are preferable.

The solvent preferably has an inorganic / organic value (I / O value) of 0.5 or more and a solubility parameter in the range of 16 to 40 [mJ / m ³ ] ^1/2 . More preferably, the I / O value is 0.6 to 10 and the solubility parameter is in the range of 18 to 31 [mJ / m ³ ] ^1/2 . If the I / O value is less than or equal to the upper limit value (the inorganicity is not too strong) and the solubility parameter is greater than or equal to the lower limit value, the alkali saponification rate decreases or the overall uniformity of the saponification degree is unsatisfactory. This is preferable because there is no inconvenience. On the other hand, if the I / O value is equal to or higher than the lower limit value (not too biased toward the organic side) and the solubility parameter is equal to or lower than the upper limit value, problems such as high saponification speed and easy haze formation occur. This is preferable because it is excellent in terms of overall uniformity.

  Specifically, monohydric aliphatic alcohols (for example, methanol, ethanol, propanol, butanol, pentanol, hexanol, etc.), alicyclic alkanols (for example, cyclohexanol, methylcyclohexanol, methoxycyclohexanol, cyclohexyl methanol, Cyclohexylethanol, cyclohexylpropanol, etc.), phenylalkanols (eg benzyl alcohol, phenylethanol, phenylpropanol, phenoxyethanol, methoxybenzyl alcohol, benzyloxyethanol etc.), heterocyclic alkanols (eg furfuryl alcohol, tetrahydrofurfuryl alcohol) Etc.), monoethers of glycol compounds (for example, methyl cellosolve, ethyl cellosolve, propyl cell) Rub, methoxymethoxyethanol, butyl cellosolve, hexyl cellosolve, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, ethoxytriglycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether Etc.) Ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), Amides (eg, N, N-dimethylformamide, dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, etc.) , Sulfoxides (eg, dimethyl sulfoxide) and ethers (eg, tetrahydrofuran, pyran, dioxane, trioxane, dimethyl cellosolve, diethyl) Cellosolve, dipropyl cellosolve, methyl ethyl cellosolve, dimethyl carbitol, dimethyl carbitol, methyl ethyl carbitol, etc.) and the like. The organic solvent to be used may be used alone or in combination of two or more. When organic solvents are used alone or in combination of two or more, at least one organic solvent is preferably one having high solubility in water. The solubility of the organic solvent in water is preferably 50% by mass or more, and more preferably freely mixed with water. Thus, an alkaline solution having sufficient solubility in an alkali agent, a salt of a fatty acid by-produced by carrying out saponification, a carbonate salt generated by absorbing carbon dioxide in the air, and the like can be prepared.

The alkaline solution used in the present invention preferably contains a surfactant such as an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or a fluorosurfactant.
In addition, the alkaline solution used in the present invention preferably contains a compatibilizing agent such as a water-soluble polymer containing a repeating unit having a hydroxyl group and / or an amide group such as a polyol compound or a saccharide.

<< The process of putting the photocurable resin layer of the photosensitive film on the alkali-treated surface of the flexible support and press-bonding >>
In the production method of the present invention, the photocurable resin layer of a photosensitive film having a photocurable resin layer is superimposed on a temporary support on the alkali-treated surface of the flexible support, and then pressure-bonded. Process.

(Photosensitive film)
Next, the photosensitive film used for the manufacturing method of this invention is demonstrated.
The photosensitive film includes a photocurable resin layer on a temporary support.
Furthermore, it is preferable that the photosensitive film in this invention has a thermoplastic resin layer between a temporary support body and a photocurable resin layer. That is, in the production method of the present invention, the photosensitive film preferably has at least the temporary support, the thermoplastic resin layer, and the photocurable resin layer in this order. When a mask layer or the like is formed using the photosensitive film having the thermoplastic resin layer, bubbles are less likely to be generated in the element formed by transferring the photocurable resin layer, and image unevenness occurs in the image display device. This makes it difficult to obtain excellent display characteristics.
The photosensitive film used in the present invention may be a negative material or a positive material.

<Temporary support>
As the temporary support, a material that is flexible and does not cause significant deformation, shrinkage, or elongation under pressure or under pressure and heating 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 particularly preferable.

There is no restriction | limiting in particular in the thickness of a temporary support body, The range of 5-200 micrometers is common, and the range of 10-150 micrometers is especially preferable at points, such as handleability and versatility.
Further, the temporary support may be transparent or may contain dyed silicon, alumina sol, chromium salt, zirconium salt or the like.
Further, the temporary support used in the production method of the present invention can be imparted with conductivity by the method described in JP-A-2005-221726.

<Thermoplastic resin layer>
The photosensitive film in the present invention is preferably provided with a thermoplastic resin layer between the temporary support and the colored photosensitive resin layer. The thermoplastic resin layer is preferably alkali-soluble. The thermoplastic resin layer plays a role as a cushioning material so as to be able to absorb unevenness of the base surface (including unevenness due to already formed images, etc.), and according to the unevenness of the target surface. It is preferable to have a property that can be deformed.

  The thermoplastic resin layer preferably includes an organic polymer substance described in JP-A-5-72724 as a component. The Vicat method [specifically, a polymer by American Material Testing Method ASTM D1235] An embodiment containing at least one selected from organic polymer substances having a softening point of about 80 ° C. or less according to the softening point measurement method] is particularly preferable.

  Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers with ethylene and vinyl acetate or saponified products thereof, copolymers of ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride and vinyl chloride, Vinyl chloride copolymer with vinyl acetate or saponified product thereof, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer with styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, Vinyl toluene copolymer of vinyl toluene and (meth) acrylic acid ester or saponified product thereof, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer weight of butyl (meth) acrylate and vinyl acetate, etc. Coalescence, vinyl acetate copolymer nylon, copolymer nylon, - alkoxymethyl nylon, and organic polymers such as polyamide resins such as N- dimethylamino nylon.

  The layer thickness of the thermoplastic resin layer is preferably 3 to 30 μm. When the thickness of the thermoplastic resin layer is less than 3 μm, followability at the time of lamination may be insufficient, and unevenness on the base surface may not be completely absorbed. In addition, when the layer thickness exceeds 30 μm, a load is applied to drying (solvent removal) at the time of forming the thermoplastic resin layer on the temporary support, or it takes time to develop the thermoplastic resin layer, May deteriorate process suitability. The layer thickness of the thermoplastic resin layer is more preferably 4 to 25 μm, and particularly preferably 5 to 20 μm.

  The thermoplastic resin layer can be formed by applying a preparation liquid containing a thermoplastic organic polymer, and the preparation liquid used for the application can be prepared using a solvent. The solvent is not particularly limited as long as it can dissolve the polymer component constituting the layer, and examples thereof include methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, and 2-propanol.

<Photocurable resin layer>
The photosensitive film in this invention comprises a photocurable resin layer. Moreover, an additive can be added to a photocurable resin layer according to the use. That is, when using the said photosensitive film for formation of a mask layer, a coloring agent can be contained in a photocurable resin layer. Moreover, when the photosensitive film in this invention has a conductive photocurable resin layer, a conductive fiber etc. can be contained in the said photocurable resin layer.

  When the photosensitive film in the present invention is a negative material, the photocurable resin layer may contain a photocurable resin (preferably an alkali-soluble resin), a polymerizable compound, a polymerization initiator, or a polymerization initiation system. preferable. In addition, colorants, additives, and the like are used, but are not limited thereto.

As said photocurable resin contained in the photosensitive film used for this invention, Paragraph [0025] of Unexamined-Japanese-Patent No. 2011-95716 and Paragraph [0033]-[0052] of Unexamined-Japanese-Patent No. 2010-237589 are described. Polymers can be used. Among them, the production method of the present invention is characterized in that the photocurable resin layer contains a carboxylic acid group-containing resin to improve adhesion with at least one surface of the alkali-treated flexible support. To preferred.
As the polymerizable compound, the polymerizable compounds described in paragraphs [0023] to [0024] of Japanese Patent No. 4098550 can be used.
As the polymerization initiator or polymerization initiation system, the polymerizable compounds described in [0031] to [0042] described in JP2011-95716A can be used.

(Conductive photocurable resin layer (conductive fiber))
When the photosensitive film of the present invention in which the conductive photocurable resin layer is laminated is used for forming a transparent electrode pattern or another conductive element, the following conductive fibers are used for the photocurable resin layer. be able to.

There is no restriction | limiting in particular as a structure of an electroconductive fiber, Although it can select suitably according to the objective, A solid structure or a hollow structure is preferable.
Here, the fiber having a solid structure may be referred to as “wire”, and the fiber having a hollow structure may be referred to as “tube”. In addition, a conductive fiber having an average minor axis length of 5 nm to 1,000 nm and an average major axis length of 1 μm to 100 μm may be referred to as “nanowire”.
In addition, conductive fibers having an average minor axis length of 1 nm to 1,000 nm, an average major axis length of 0.1 μm to 1,000 μm, and having a hollow structure may be referred to as “nanotubes”.
The material of the conductive fiber is not particularly limited as long as it has conductivity, and can be appropriately selected according to the purpose. However, at least one of metal and carbon is preferable, and among these, The conductive fiber is particularly preferably at least one of metal nanowires, metal nanotubes, and carbon nanotubes.

--- Metal nanowires--
-Metal-
The material of the metal nanowire is not particularly limited. For example, at least one metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the long periodic table (IUPAC 1991) is preferable. More preferably, at least one metal selected from Group 2 to Group 14 is selected from Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, and Group 14. At least one metal selected from the group is more preferable, and it is particularly preferable to include it as a main component.

Examples of the metal include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, antimony, and lead. And alloys thereof. Among these, in view of excellent conductivity, those mainly containing silver or those containing an alloy of silver and a metal other than silver are preferable.
Containing mainly silver means that the metal nanowire contains 50% by mass or more, preferably 90% by mass or more.
Examples of the metal used in the alloy with silver include platinum, osmium, palladium and iridium. These may be used alone or in combination of two or more.

-Shape-
There is no restriction | limiting in particular as a shape of the said metal nanowire, According to the objective, it can select suitably, For example, it can take arbitrary shapes, such as a column shape, a rectangular parallelepiped shape, and the column shape from which a cross section becomes a polygon. In applications where high transparency is required, a cylindrical shape and a cross-sectional shape with rounded polygonal corners are preferred.
The cross-sectional shape of the metal nanowire can be examined by applying a metal nanowire aqueous dispersion on a substrate and observing the cross-section with a transmission electron microscope (TEM).
The corner of the cross section of the metal nanowire means a peripheral portion of a point that extends each side of the cross section and intersects with a perpendicular drawn from an adjacent side. Further, “each side of the cross section” is a straight line connecting these adjacent corners. In this case, the ratio of the “outer peripheral length of the cross section” to the total length of the “each side of the cross section” was defined as the sharpness. For example, in the metal nanowire cross section as shown in FIG. 9, the sharpness can be represented by the ratio of the outer peripheral length of the cross section indicated by the solid line and the outer peripheral length of the pentagon indicated by the dotted line. A cross-sectional shape having a sharpness of 75% or less is defined as a cross-sectional shape having rounded corners. The sharpness is preferably 60% or less, and more preferably 50% or less. If the sharpness exceeds 75%, the electrons may be localized at the corners, and plasmon absorption may increase, or the transparency may deteriorate due to yellowing or the like. Moreover, the linearity of the edge part of a pattern may fall and a shakiness may arise. The lower limit of the sharpness is preferably 30%, more preferably 40%.

−Average minor axis length diameter and average major axis length−
The average minor axis length of the metal nanowire (sometimes referred to as “average minor axis diameter” or “average diameter”) is preferably 150 nm or less, more preferably 1 nm to 40 nm, still more preferably 10 nm to 40 nm, 15 nm to 35 nm is particularly preferable.
When the average minor axis length is less than 1 nm, the oxidation resistance may be deteriorated and the durability may be deteriorated. When the average minor axis length is more than 150 nm, scattering due to metal nanowires occurs and sufficient transparency is obtained. There are times when you can't.
The average minor axis length of the metal nanowires was observed from 300 metal nanowires using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). The average minor axis length of was determined. In addition, the shortest axis length when the short axis of the metal nanowire is not circular is the shortest axis.

The average major axis length of the metal nanowire (sometimes referred to as “average length”) is preferably 1 μm to 40 μm, more preferably 3 μm to 35 μm, and even more preferably 5 μm to 30 μm.
If the average major axis length is less than 1 μm, it may be difficult to form a dense network and sufficient conductivity may not be obtained. If it exceeds 40 μm, the metal nanowires are too long and manufactured. Sometimes entangled and agglomerates may occur during the manufacturing process.
The average major axis length of the metal nanowires is, for example, observed with 300 metal nanowires using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). The average major axis length of the wire was determined. In addition, when the said metal nanowire was bent, the circle | round | yen which makes it an arc was considered and the value calculated from the radius and curvature was made into the major axis length.

  The thickness of the conductive photocurable resin layer is preferably from 0.1 to 20 μm, and preferably from 0.5 to 18 μm, from the viewpoint of process suitability such as the stability of the coating liquid and drying during coating and development time during patterning. More preferably, 1-15 micrometers is especially preferable. The content of the conductive fiber relative to the total solid content of the conductive photocurable resin layer is preferably 0.01 to 50% by mass, and 0.05 to 30% by mass from the viewpoint of conductivity and stability of the coating liquid. % Is more preferable, and 0.1 to 20% by mass is particularly preferable.

(Mask layer (colorant))
Moreover, when using the photocurable resin layer of the photosensitive film used for this invention as a mask layer of an electrostatic capacitance type input device, a coloring agent can be used for a photocurable resin layer. As the colorant used in the present invention, known colorants (organic pigments, inorganic pigments, dyes, etc.) can be suitably used. In the present invention, in addition to the black colorant, a mixture of pigments such as red, blue, and green can be used.

In the production method of the present invention, the photocurable resin layer preferably contains at least one of a black colorant and a white colorant.
When using the said photocurable resin layer as a black mask layer, it is preferable that a black coloring agent is included from a viewpoint of optical density. Examples of the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, and graphite. Among these, carbon black is preferable.

  When the photo-curable resin layer is used as a white mask layer, the white pigment described in paragraphs [0015] and [0114] of JP-A-2005-7765 can be used. For use as a mask layer of other colors, pigments or dyes described in paragraphs [0183] to [0185] of Japanese Patent No. 4546276 may be mixed and used. Specifically, the pigments and dyes described in paragraphs [0038] to [0054] of JP-A-2005-17716, and the pigments described in paragraphs [0068] to [0072] of JP-A-2004-361447. The coloring agents described in paragraph numbers [0080] to [0088] of JP-A-2005-17521 can be suitably used.

The colorant (preferably a pigment, more preferably carbon black) is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the colorant and the pigment dispersant in an organic solvent (or vehicle) described later. The vehicle is a portion of a medium in which a pigment is dispersed when the paint is in a liquid state, and is a liquid component that binds to the pigment to form a coating film (binder) and dissolves and dilutes it. Component (organic solvent).
The disperser used for dispersing the pigment is not particularly limited. For example, the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described on page 310 of the document.

  From the viewpoint of dispersion stability, the colorant used in the present invention preferably has a number average particle diameter of 0.001 μm to 0.1 μm, and more preferably 0.01 μm to 0.08 μm. The “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for a large number of particles, This 100 average value is said.

The layer thickness of the photocurable resin layer containing the colorant is preferably 0.5 to 10 μm, more preferably 0.8 to 5 μm, and particularly preferably 1 to 3 μm from the viewpoint of a difference in thickness from the other layers. Although there is no restriction | limiting in particular as content rate of the coloring agent in solid content of the coloring photosensitive resin composition in this invention, It is preferable that it is 15-70 mass% from a viewpoint of fully shortening development time, 20 More preferably, it is -60 mass%, and it is still more preferable that it is 25-50 mass%.
The total solid content as used in this specification means the total mass of the non-volatile component remove | excluding the solvent etc. from the coloring photosensitive resin composition.

(Insulating layer)
In addition, when forming an insulating layer using the said photosensitive film, 0.1-5 micrometers is preferable from a viewpoint of maintenance of insulation, and, as for the layer thickness of a photocurable resin layer, 0.3-3 micrometers is still more preferable. 0.5-2 μm is particularly preferable.

(Transparent protective layer)
When forming a transparent protective layer using the said photosensitive film, the layer thickness of a photocurable resin layer is 0.5-10 micrometers from a viewpoint of exhibiting sufficient surface protection ability, and 0.8-5 micrometers is preferable. Further preferred is 1 to 3 μm.

<Additives>
Furthermore, an additive may be used for the photocurable resin layer. Examples of the additive include surfactants described in paragraph [0017] of Japanese Patent No. 4502784, paragraphs [0060] to [0071] of JP-A-2009-237362, and paragraph [ And the other additives described in paragraphs [0058] to [0071] of JP-A No. 2000-310706.
Moreover, as a solvent at the time of manufacturing the photosensitive film in this invention by application | coating, the solvent as described in Paragraph [0043]-[0044] of Unexamined-Japanese-Patent No. 2011-95716 can be used.

  As mentioned above, although the case where the photosensitive film in this invention was a negative type material was demonstrated centering, the positive type material may be sufficient as the said photosensitive film. When the photosensitive film is a positive material, for example, a material described in JP-A-2005-221726 is used for the photocurable resin layer, but the material is not limited thereto.

(Viscosity of thermoplastic resin layer and photocurable resin layer)
The viscosity measured at 100 ° C. of the thermoplastic resin layer in the present invention is in the region of 1000 to 10,000 Pa · sec, the viscosity measured at 100 ° C. of the photocurable resin layer is in the region of 2000 to 50000 Pa · sec, and It is preferable to satisfy the formula (A).
Formula (A): Viscosity of thermoplastic resin layer <viscosity of photocurable resin layer

  Here, the viscosity of each layer can be measured as follows. The solvent is removed from the coating solution for the thermoplastic resin layer or the photocurable resin layer by drying under atmospheric pressure and reduced pressure to obtain a measurement sample. For example, as a measuring instrument, Vibron (DD-III type: manufactured by Toyo Baldwin Co., Ltd.) Can be used under the conditions of a measurement start temperature of 50 ° C., a measurement end temperature of 150 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz / deg, and a measurement value of 100 ° C. can be used.

<Other layers>
For the photosensitive film used in the present invention, an intermediate layer is provided between the photocurable resin layer and the thermoplastic resin layer, or a protective film is further provided on the surface of the photocurable resin layer. Can be configured.

  In the photosensitive film used in the present invention, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during the application of a plurality of layers and during storage after the application. As the intermediate layer, an oxygen barrier film having an oxygen barrier function, which is described as “separation layer” in JP-A-5-72724, is preferable, which increases the sensitivity during exposure and reduces the time load of the exposure machine. And productivity is improved.

  As the intermediate layer and the protective film, those described in paragraphs [0083] to [0087] and [0093] of JP-A-2006-259138 can be appropriately used.

<Method for producing photosensitive film>
The photosensitive film in the present invention can be produced according to the method for producing a photosensitive transfer material described in paragraphs [0094] to [0098] of JP-A-2006-259138.
When the photosensitive film of the present invention having an intermediate layer is specifically formed, a solution (thermoplastic resin layer coating solution) in which an additive is dissolved together with a thermoplastic organic polymer is formed on a temporary support. After coating and drying to provide a thermoplastic resin layer, a prepared solution (intermediate layer coating solution) prepared by adding a resin or an additive to a solvent that does not dissolve the thermoplastic resin layer on this thermoplastic resin layer The intermediate layer is applied by coating and drying, and a coating solution for a colored photosensitive resin layer prepared using a solvent that does not dissolve the intermediate layer is further applied onto the intermediate layer, and the colored photosensitive resin layer is dried and applied. Can be suitably produced.

<Cover film removal process>
A cover film that removes the cover film when the photosensitive film has a cover film before the method of laminating and pressure-bonding the photocurable resin layer of the photosensitive film on the alkali-treated surface of the flexible support. It is preferable to include a removal step.

<The process of laminating | stacking and crimping | bonding the photocurable resin layer of a photosensitive film on the alkali-treated surface of a flexible support body>
Pressure bonding (also referred to as bonding or transfer) on the alkali-treated surface of the flexible support of the photocurable resin layer was performed by subjecting the photocurable resin layer to an alkali treatment of the flexible support. This is done by applying pressure on the surface.
The linear pressure in the crimping step is preferably 60 to 200 N / cm, more preferably 70 to 160 N / cm, and particularly preferably 80 to 120 N / cm.
The conveyance speed in the crimping step is preferably 0.3 to 10 m / min, more preferably 0.4 to m / min, and particularly preferably 0.5 to 3 m / min.
For laminating, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
Moreover, it is preferable that the manufacturing method of this invention overlaps so that the alkali-treated surface of a flexible support body and the photocurable resin layer of a photosensitive film may adjoin. That is, since the surface of the flexible support is alkali-treated in the production method of the present invention, the photocurable resin layer of the photosensitive film and the flexible support are not required to overlap with each other through an adhesive or a pressure-sensitive adhesive. Adhesiveness can be improved.

In the production method of the present invention, it is preferable to perform the pressure-bonding step while heating.
The heating temperature in the crimping step is preferably 50 to 140 ° C, more preferably 60 to 120 ° C, and particularly preferably 70 to 100 ° C.

  It is preferable to remove the temporary support after a step (hereinafter also referred to as a transfer step) in which the photocurable resin layer of the photosensitive film is stacked on the surface of the flexible support that has been subjected to alkali treatment and pressure-bonded.

[Capacitance type input device and manufacturing method thereof]
The capacitance-type input device of the present invention includes a cured product laminate formed by exposing a laminate having a photocurable resin layer produced by the method for producing a laminate having the photocurable resin layer of the invention. It is characterized by that.
Moreover, the manufacturing method of the capacitance-type input device of this invention has the process of exposing the laminated body which has the photocurable resin layer manufactured with the manufacturing method of the laminated body which has the photocurable resin layer of this invention. It is characterized by including.
Hereinafter, the capacitance-type input device of the present invention and the manufacturing method thereof will be described.

  The capacitive input device of the present invention preferably has a mask layer, and at least one layer of the cured product laminate is preferably the mask layer. That is, the method for manufacturing a capacitance-type input device of the present invention is a method for manufacturing a capacitance-type input device having a mask layer. The laminate having the photocurable resin layer is exposed to expose the mask layer. It is preferable to form.

The capacitance-type input device of the present invention preferably includes the following elements (1) to (5), and at least one layer of the cured product laminate is the (1) mask layer. That is, the manufacturing method of the capacitive input device of the present invention is a manufacturing method of a capacitive input device having the following elements (1) to (5), and a laminate having the photocurable resin layer: It is preferable to form the mask layer by exposing (1).
(1) Mask layer (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (3) The first transparent electrode pattern and the electric A plurality of second transparent electrode patterns comprising a plurality of pad portions that are electrically insulated and extend in a direction intersecting the first direction (4) The first transparent electrode pattern and the second An insulating layer that electrically insulates the transparent electrode pattern (5) electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern, and the first transparent electrode pattern and the second transparent electrode pattern Conductive element separate from the second transparent electrode pattern

<Configuration of capacitance type input device>
First, the configuration of the capacitive input device of the present invention formed by the manufacturing method of the present invention will be described. 1A to 1D are cross-sectional views showing the configuration of the capacitive input device of the present invention.
In FIG. 1A, a capacitive input device 10 includes a flexible support 1, a first transparent electrode pattern 3, a second transparent electrode pattern 4, a conductive element 6, a transparent protective layer 7, It is composed of a transparent adhesive layer 14, a front plate (glass) 1 ′, a mask layer 2, and a cover glass 13.
In FIG. 1B, the capacitive input device 10 includes a flexible support 1, a first transparent electrode pattern 3, a second transparent electrode pattern 4, an insulating layer 5, a conductive element 6, and a transparent It comprises a protective layer 7, a transparent adhesive layer 14, a front plate (glass) 1 ′, a mask layer 2, and a cover glass 13.
1C, the capacitive input device 10 includes a flexible support 1, a mask layer 2, a first transparent electrode pattern 3, a second transparent electrode pattern 4, an insulating layer 5, and a conductive property. It is comprised from the element 6, the transparent protective layer 7, the transparent adhesive bond layer (not shown), and the front board (glass) 1 '.
1D, the capacitive input device 10 includes a flexible support 1, a mask layer 2, a first transparent electrode pattern 3, a second transparent electrode pattern 4, an insulating layer 5, and a conductive property. It is composed of an element 6 and a transparent protective layer 7.

The flexible support 1 is a flexible support in the production method of the present invention. The capacitance-type input device of the present invention can achieve thinning / lightening by using the flexible support 1.
In particular, the capacitive input device of the present invention achieves a significant reduction in thickness and weight by using the flexible support 1 instead of the front plate (glass) 1 ′ described later. be able to. In the capacitance-type input device 10 of the present invention having such a configuration, when the flexible support 1 is disposed at the outermost part, the contact surface of the flexible support 1 (each of the front layer 1) Input is performed by bringing a finger or the like into contact with the element (the side opposite to the non-contact surface).
However, the capacitance-type input device of the present invention may also have a front plate (glass) 1 ′ in addition to the flexible support 1, and even in that case, only the front plate (glass) 1 ′ is included. Compared with the case where it is used as a substrate, it is possible to achieve a reduction in thickness / weight. When forming a transparent electrode pattern on a glass substrate by forming a black layer on a flexible support, the entire device is thinner than when forming both a black layer and a transparent electrode pattern on glass for the following reasons. Layer / weight reduction can be achieved. Since the strength of the front plate is increased by bonding the flexible support on which the black layer is formed to the front plate, the front plate can be made thinner / lighter.

  The front plate 1 is composed of a light-transmitting substrate such as a glass substrate, and tempered glass represented by Corning gorilla glass can be used. In the capacitive input device 10 of the present invention, when the front plate 1 is arranged outside the flexible support 1, the contact surface of the front plate 1 ′ (the surface opposite to the non-contact surface). An input is performed by touching a finger or the like.

  Further, the flexible support 1 and / or the front plate 1 ′ may be provided with an opening 8 in part as shown in FIG. 2. A mechanical switch by pressing can be installed in the opening 8.

Moreover, it is preferable that the electrostatic capacitance type input device of this invention is provided with the mask layer 2, and at least 1 layer of the hardened | cured material laminated body formed by exposing the laminated body which has the said photocurable resin layer is a mask layer. It is preferable that The mask layer 2 is a frame-shaped pattern around the display area formed on the non-contact side of the front panel of the touch panel, and is formed so that the lead wiring and the like cannot be seen.
In the capacitive input device 10 of the present invention, as shown in FIG. 2, a mask layer 2 is provided so as to cover a part of the frame region (region other than the input surface in FIG. 2). It is preferable.

A plurality of first transparent electrode patterns in which a plurality of pad portions extend in a first direction via connection portions on the non-contact surface of the flexible support 1 and / or the front plate 1 ′. 3 and a plurality of second transparent electrode patterns 4 that are formed of a plurality of pad portions that are electrically insulated from the first transparent electrode pattern 3 and extend in a direction crossing the first direction, It is preferable that an insulating layer 5 that electrically insulates the first transparent electrode pattern 3 and the second transparent electrode pattern 4 is formed as necessary. The first transparent electrode pattern 3, the second transparent electrode pattern 4, and the conductive element 6 to be described later are, for example, translucent conductive materials such as ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide). It can be made of a conductive metal oxide film. Examples of such metal films include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO ₂ . At this time, the film 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. Moreover, said 1st transparent electrode pattern 3, the 2nd transparent electrode pattern 4, and the electroconductive element 6 are manufactured using the photosensitive film which has the photocurable resin layer using the said electroconductive fiber. You can also. In addition, when the first conductive pattern or the like is formed of ITO or the like, paragraphs [0014] to [0016] of Japanese Patent No. 4506785 can be referred to.

  In addition, at least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4 is a non-contact surface of the flexible support 1 and / or the front plate 1 ′ and the flexible support of the mask layer 2. It can be installed across both areas of the body 1 and / or the surface opposite the front plate 1 '. In FIG. 1C and FIG. 1D, the second transparent electrode pattern extends over both the non-contact surface of the flexible support 1 and the region of the mask layer 2 opposite to the flexible support 1. The installed figure is shown. As described above, even when a photosensitive film is laminated across the mask layer requiring a certain thickness and the back surface of the flexible support, a vacuum laminator can be obtained by using the photosensitive film having a specific layer structure of the present invention. Even without using expensive equipment such as the above, it is possible to perform lamination without generating bubbles at the boundary of the mask portion with a simple process.

  The first transparent electrode pattern 3 and the second transparent electrode pattern 4 will be described with reference to FIG. FIG. 3 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern in the present invention. As shown in FIG. 3, the first transparent electrode pattern 3 is formed such that the pad portion 3a extends in the first direction via the connection portion 3b. The second transparent electrode pattern 4 is electrically insulated by the first transparent electrode pattern 3 and the insulating layer 5 and extends in a direction intersecting the first direction (second direction in FIG. 3). It is constituted by a plurality of pad portions that are formed. Here, when the first transparent electrode pattern 3 is formed, the pad portion 3a and the connection portion 3b may be manufactured as one body, or only the connection portion 3b is manufactured and the pad portion 3a and the second portion 3b are formed. The transparent electrode pattern 4 may be integrally formed (patterned). When the pad portion 3a and the second transparent electrode pattern 4 are manufactured (patterned) as a single body (patterning), as shown in FIG. Each layer is formed so that the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are electrically insulated by 5.

  1A to 1D, the conductive element 6 is disposed on the orthogonal projection of the mask layer 2. The 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 is different from the first transparent electrode pattern 3 and the second transparent electrode pattern 4. Is another element. In FIGS. 1A to 1D, diagrams in which the conductive element 6 is connected to the second transparent electrode pattern 4 are shown.

  Moreover, in FIG. 1A-FIG. 1D, the transparent protective layer 7 is installed so that all of each component of (1)-(5) may be covered. The transparent protective layer 7 may be configured to cover only a part of each component. The insulating layer 5 and the transparent protective layer 7 may be made of the same material or different materials. The material constituting the insulating layer 5 and the transparent protective layer 7 is preferably a material having high surface hardness and high heat resistance, and a known photosensitive siloxane resin material, acrylic resin material, or the like is used.

In the manufacturing method of the capacitive input device of the present invention, the mask layer 2, the first transparent electrode pattern 3, the second transparent electrode pattern 4, the insulating layer 5, the conductive element 6 and the necessary Accordingly, at least one element with the transparent protective layer 7 is preferably formed using the photosensitive film of the present invention.
The mask layer 2, the insulating layer 5 and the transparent protective layer 7 can be formed by transferring a photocurable resin layer to the front plate 1 using the photosensitive film of the present invention. For example, when the black mask layer 2 is formed, the black light curing is performed on the surface of the front plate 1 using the photosensitive film having the black photocurable resin layer as the photocurable resin layer. It can be formed by transferring the conductive resin layer. When the insulating layer 5 is formed, the front plate on which the first transparent electrode pattern is formed using the photosensitive film having an insulating photocurable resin layer as the photocurable resin layer. It can be formed by transferring the photocurable resin layer to the surface of 1. Even when the transparent protective layer 7 is formed, the flexible support 1 in which each element is formed using the photosensitive film according to the present invention having a transparent photocurable resin layer as the photocurable resin layer. And / or it can form by transferring the said photocurable resin layer to the surface of front plate 1 '.

Moreover, although there is no restriction | limiting in particular in the size of the said mask layer 2 formed using the said photosensitive film by the manufacturing method of this invention, it is a mask to the boundary limit of the flexible support body 1 and / or front plate 1 '. From the viewpoint of manufacturing the layer (pattern) without defects, for example, the outer periphery can be a mask layer having a thickness of 100 to 700 mm, and a mask layer having a thickness of 300 to 500 mm is preferable. Further, in the case where the mask layer has a shape as shown in FIG. 12 having a cavity in the center, from the viewpoint of manufacturing the mask layer (pattern) without defects up to the boundary of the flexible support 1 and / or the front plate 1 ′. Can be a mask layer having a pattern inner circumference of 50 to 400 mm, preferably a mask layer of 100 to 300 mm. From the same viewpoint, the area of the resulting mask layer may be a 1～150Cm ^2, it is preferable that the 30~120cm ^2.
When the mask layer 2 or the like is formed using the photosensitive film, even a substrate (front plate) having an opening has no resist component leakage from the opening, and particularly the flexible support 1 and / or the front plate 1. There is an advantage of thin layer / light weight in a simple process without contaminating the back side of the substrate because there is no protrusion of the resist component from the glass edge in the mask layer where it is necessary to form a light-shielding pattern to the end of ' The touch panel can be manufactured.
Furthermore, the formation of the mask layer 2 that requires light shielding prevents the generation of bubbles during lamination of the photosensitive film by using a photosensitive film having a thermoplastic resin layer between the photocurable resin layer and the temporary support. In addition, it is possible to form a high-quality mask layer 2 or the like without light leakage.

Said 1st transparent electrode pattern 3, the 2nd transparent electrode pattern 4, and the electroconductive element 6 can be formed using the photosensitive film in this invention which has an etching process or a conductive photocurable resin layer.
When the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 are formed by an etching process, on the non-contact surface of the flexible support 1 and / or the front plate 1 ′. A transparent electrode layer such as ITO is formed by sputtering. Next, an etching pattern is formed by exposure and development using the photosensitive film according to the present invention having an etching photocurable resin layer as the photocurable resin layer on the transparent electrode layer. Thereafter, the transparent electrode layer is etched to pattern the transparent electrode, and the etching pattern is removed, whereby the first transparent electrode pattern 3 and the like can be formed.

When the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 are formed using the photosensitive film of the present invention having a conductive photocurable resin layer, the front plate 1 It can be formed by transferring the conductive photocurable resin layer to the surface.
When the first transparent electrode pattern 3 or the like is formed using a photosensitive film having the conductive photocurable resin layer, there is no leakage of resist components from the opening portion even on a substrate (front plate) having an opening portion. Without contaminating the back side of the substrate, it is possible to manufacture a touch panel having a merit of thin layer / light weight by a simple process.
Furthermore, the photosensitive film in the present invention having a specific layer structure having a thermoplastic resin layer between the conductive photocurable resin layer and the temporary support is used for forming the first transparent electrode pattern 3 and the like. Thus, it is possible to prevent the generation of bubbles during lamination of the photosensitive film, and to form the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 with excellent conductivity and low resistance.

  As examples of the capacitive input device formed in the course of the manufacturing method of the present invention, the modes shown in FIGS. FIG. 4 is a top view illustrating an example of the tempered glass 11 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. These show examples embodying the above description, and the scope of the present invention is not limitedly interpreted by these drawings.

<Each Step of Manufacturing Method of Capacitance Type Input Device>
-Exposure process, development process, and other processes-
As examples of the exposure step, the development step, and other steps, the method described in paragraphs [0035] to [0051] of JP-A-2006-23696 can be suitably used in the present invention.

The exposure step is a step of exposing the photocurable resin layer transferred onto the substrate.
Specifically, there is a method in which a predetermined mask is disposed above the photocurable resin layer formed on the substrate, and then exposed from above the mask through the mask, the thermoplastic resin layer, and the intermediate layer. Can be mentioned.
Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photocurable resin layer (for example, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 5-200 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.

The developing step is a step of developing the exposed photocurable resin layer.
The development can be performed using a developer. The developer is not particularly limited, and known developers such as those described in JP-A-5-72724 can be used. In addition, the developer preferably has a photo-curing resin layer having a dissolution type development behavior. For example, a developer containing a compound of pKa = 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable. A small amount of an organic solvent that is miscible with may be added. Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
Further, a known surfactant can be 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. Here, the shower development will be described. The uncured portion can be removed by spraying a developer onto the photocurable resin layer after exposure. When a thermoplastic resin layer or an intermediate layer is provided, an alkaline solution having a low solubility of the photocurable resin layer is sprayed by a shower or the like before development to remove the thermoplastic resin layer or the intermediate layer. It is preferable to keep it. Further, after development, it is preferable to remove the development residue while spraying ultrapure water under pressure or 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., and the pH of the developer is preferably 8 to 13.

  The manufacturing method of the capacitance-type input device of the present invention may have other processes such as a post-exposure process and a post-bake process.

  In the capacitance-type input device of the present invention, it is preferable that the cured product laminate is patterned. That is, in the method for manufacturing a capacitance-type input device of the present invention, it is preferable that patterning exposure is performed on the laminate having the photocurable resin layer. According to the method for producing a laminate having a photocurable resin layer of the present invention, pattern defects of a cured laminate obtained by patterning can be reduced. Specifically, substrate peripheral edge defects, substrate inner periphery Pattern defects and pinholes in the pattern can be reduced. Moreover, since it is excellent also in the adhesiveness of a flexible support body and a photocurable resin layer, such a pattern is also excellent in adhesiveness.

The patterning exposure may be performed after the temporary support is peeled off, or may be exposed before the temporary support is peeled off, 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 mask used for the patterning exposure is not particularly limited. However, according to the method for manufacturing a capacitance-type input device of the present invention, defects are reduced even in a mask having a fine line pattern of 10 to 50 μm. Even with a mask with a thickness of 10 to 40 μm, defects can be reduced, and even with a mask with a thickness of 10 to 20 μm, defects can be reduced.

  Also when using the photosensitive film in this invention as an etching resist (etching pattern), a resist pattern can be obtained like the said method. For the etching, etching and resist stripping can be applied by a known method described in paragraphs [0048] to [0054] of JP 2010-152155 A.

  For example, as an etching method, a commonly performed wet etching method in which the substrate is immersed in an etching solution can be used. As an etching solution used for wet etching, an acid type or an alkaline type may be appropriately selected according to an object to be etched. Examples of acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and mixed aqueous solutions of acidic components and salts of ferric chloride, ammonium fluoride, potassium permanganate, and the like. Is done. As the acidic component, a combination of a plurality of acidic components may be used. In addition, alkaline type etching solutions include sodium hydroxide, potassium hydroxide, ammonia, organic amines, aqueous solutions of alkali components such as organic amine salts such as tetramethylammonium hydroxide, alkaline components and potassium permanganate. A mixed aqueous solution of a salt such as A combination of a plurality of alkali components may be used as the alkali component.

The temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower. The resin pattern used as an etching mask (etching pattern) in the present invention is formed by using the above-described photocurable resin layer, so that it is particularly suitable for acidic and alkaline etching solutions in such a temperature range. Excellent resistance. Therefore, the resin pattern is prevented from peeling off during the etching process, and the portion where the resin pattern does not exist is selectively etched.
After the etching, a cleaning process and a drying process may be performed as necessary to prevent line contamination. For the cleaning process, the substrate is cleaned with pure water for 10 to 300 seconds at room temperature, for example, and for the drying process, air blow pressure (about 0.1 to 5 kg / cm ² ) is appropriately adjusted using air blow. Just do it.

<< Capacitance Input Device and Image Display Device Comprising Capacitance Input Device as Components >>
An electrostatic capacitance type input device obtained by the manufacturing method of the present invention and an image display device including the electrostatic capacitance type input device as a constituent element are “latest touch panel technology” (issued July 6, 2009, Inc.) Techno Times), supervised by Yuji Mitani, "Touch Panel Technology and Development", CM Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. Can be applied.

  Hereinafter, a method for manufacturing a capacitance-type input device and an image display device using the method for forming a photocurable resin layer of the present invention will be specifically described with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]
(Preparation of cellulose acylate film (CAF-1))
A flexible film (cellulose acylate film) CAF-1 having a thickness of 80 μm was produced by the following method described in JP-A-2006-307056 [0237] to [0243].
The following composition was put into a mixing tank and stirred while heating at 30 ° C. to dissolve each component to prepare a cellulose acylate solution (SA-1) (inner layer dope and outer layer dope).
Regarding the silica fine particles of the cellulose acylate solution for the outer layer, 20 parts by mass of the following silica fine particles and 80 parts by mass of methanol were thoroughly stirred for 30 minutes to obtain a mixed silica molecular dispersion.

Cellulose acylate (SA-1) solution composition Cellulose acylate solution composition For inner layer For outer layer (unit: parts by mass)
Cellulose acetate with acyl substitution degree 2.87 100 100
Triphenyl phosphate (plasticizer) 7.8 7.8
Biphenyl diphenyl phosphate (plasticizer) 3.9 3.9
Methylene chloride (first solvent) 293 314
Methanol (second solvent) 71 76
1-butanol (third solvent) 1.5 1.6
Silica fine particles (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.)
0 0.8
Retardation adjuster A 1.50

Retardation adjuster A

  When the particle size distribution of the silica fine particle dispersion was measured for the obtained outer layer dope, the particle size of 500 nm or more was 0%. Here, the volume average particle diameter was measured with a “particle size distribution measuring apparatus LA920 (manufactured by Horiba, Ltd.)”.

(Preparation of cellulose acylate film)
The obtained inner layer dope and outer layer dope were cast on a drum cooled to −5 ° C. using a three-layer co-casting die.
The drum had an arithmetic average roughness (Ra) of 0.006 μm, a maximum height (Ry) of 0.06 μm, and a ten-point average roughness (Rz) of 0.009 μm. The arithmetic average roughness (Ra), maximum height (Ry), and ten-point average roughness (Rz) were measured according to JIS B 0601.
The film having a residual solvent amount of 70% by mass was peeled off from the drum, and dried at 80 ° C. while being transported with the draw ratio in the transport direction being 110% while holding both ends with a pin tenter, and the residual solvent amount was 10%. By the way, it was dried at 110 ° C. Thereafter, it was dried at a temperature of 140 ° C. for 30 minutes to prepare a cellulose acylate film (CAF-1, outer layer: 3 μm, inner layer: 74 μm, outer layer: 3 μm) having a residual solvent of 0.3% by mass. The obtained CAF-1 had a width of 1340 mm and a thickness of 80 μm.

<Alkali saponification treatment>
Subsequently, one side of the film CAF-1 was subjected to alkali saponification treatment by the following method described in JP-A-2006-307056 [0249] to [0250], and the alkali-treated flexible support CFS- 01 was obtained.
That is, after passing the film (flexible support CAF-1) on a dielectric heating roll having a temperature of 60 ° C. and raising the film surface temperature to 40 ° C., an alkali solution (S-1) having the composition shown below is used. ) Was applied at a coating amount of 17 mL / m ² using a rod coater, and was allowed to stay for 10 seconds under a steam far-infrared heater manufactured by Noritake Company Limited, heated to 110 ° C. Subsequently, a surface saponified film is obtained by using the same rod coater to carry out a step of scraping with an alkali diluted solution that is a 10% isopropyl alcohol aqueous solution and a coating amount of 2.8 mL / m ² (liquid amount on the secondary side of the coater) after scraping. A sample (CFS-01) was prepared. The film temperature was 40 ° C. Next, washing with a fountain coater (washing water temperature: 40 ° C.) and draining with an air knife were repeated four times, and then the mixture was retained in a drying zone at 70 ° C. for 5 seconds and dried.

(Alkaline solution (S-1) composition)
Potassium hydroxide 8.6 parts by mass Water 24.1 parts by mass Isopropanol 56.3 parts by mass Surfactant (K-1: C ₁₆ H ₃₃ O (CH ₂ CH ₂ O) ₁₀ H) 1.0 part by mass Propylene glycol 10.0 parts by mass

<Production of photosensitive film>
By the following method, the photosensitive film K1 which comprises a temporary support body, a thermoplastic resin layer, an intermediate | middle layer, a black photocurable resin layer, and a protective film in this order was produced.
On a polyethylene terephthalate film (temporary support) having a thickness of 75 μm, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Further, the black composition K1 was applied and dried. In this way, the thermoplastic film layer having a dry film thickness of 15.1 μm, the intermediate layer having a dry film thickness of 1.6 μm, and the dry film thickness so that the optical density is 4.0 are formed on the temporary support. A 2.2 μm black photocurable resin layer was provided, and finally a protective film (12 μm thick polypropylene film) was pressure-bonded. In this way, a photosensitive film (transfer material) in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black photocurable resin layer are integrated is produced, and the sample name is black. It was set as K1.

(Coating solution for thermoplastic resin layer: Formulation H1)
Methanol: 11.1 parts by mass Propylene glycol monomethyl ether acetate: 6.36 parts by mass Methyl ethyl ketone: 52.4 parts by mass Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio) (Molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg≈70 ° C.): 5.83 parts by mass Styrene / acrylic acid copolymer (copolymerization composition ratio (mol) Ratio) = 63/37, weight average molecular weight = 10,000, Tg≈100 ° C.): 13.6 parts by mass. 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (Shin Nakamura Chemical Co., Ltd.) )): 9.1 parts by mass. Fluoropolymer: 0.54 parts by mass (C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = CH ₂ 40 parts and H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH═CH ₂ 55 parts and H (OCHCH ₂ ) ₇ OCOCH═CH ₂ 5 parts copolymer, weight average molecular weight 30,000, methyl ethyl ketone 30 mass% solution, manufactured by Dainippon Ink & Chemicals, Inc. Name: Mega Fuck F780F)

(Coating liquid for intermediate layer: prescription P1)
PVA205: 32.2 parts by mass (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 550)
Polyvinylpyrrolidone: 14.9 parts by mass (manufactured by IPS Japan, K-30)
-Distilled water: 524 parts by mass-Methanol: 429 parts by mass

  The alkali-treated flexible film CFS-01 was heated with a substrate preheating device at 80 ° C. for 2 minutes, and the protective film was removed from the black photosensitive film K1.

<Manufacture of a laminate having a photocurable resin layer>
Laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)) is superposed so that the surface of the black photocurable resin layer exposed after removal and the alkali-treated surface of the flexible support CFS-01 are in contact with each other. Was laminated at a rubber roller temperature of 100 ° C., a linear pressure of 100 N / cm, and a conveying speed of 1.0 m / min. The laminated body which has the obtained flexible support body, a black photocurable resin layer, an intermediate | middle layer, a thermoplastic resin layer, and a temporary support body in this order was photocurability manufactured with the manufacturing method of Example 1. A laminate having a resin layer was obtained.

[Evaluation]
The black pattern A and the black pattern B were manufactured according to the following method using the laminated body which has the photocurable resin layer manufactured with the manufacturing method of Example 1, and the following evaluation was performed.

<Pattern missing evaluation using black pattern A>
(Manufacture of black pattern A)
From the laminate having the photocurable resin layer produced by the production method of Example 1, the polyethylene terephthalate temporary support was peeled off at the interface with the thermoplastic resin layer to remove the temporary support.
A substrate obtained by removing the temporary support from the laminate having the photocurable resin layer of Example 1 with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp after peeling the temporary support. 11 with the mask A, which is a quartz exposure mask having the mask pattern shown in FIG. The distance between the conductive resin layers was set to 200 μm, and pattern exposure was performed with an exposure amount of 70 mJ / cm ² . Mask A is for pattern loss evaluation. In the light transmission pattern portion 24 of FIG. 11, the light shielding portion is not shown, but the mask pattern shown in FIG. 10 is formed. Specifically, the light transmission pattern portion 24 in the mask A is configured such that the light shielding portion 23 having a size of 1 mm (1000 μm) in both vertical and horizontal directions is arranged with a gap size of 50 μm between the light shielding portions 23.

  Next, a triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) 12 times with pure water (1 part by mass of T-PD2 and pure water 11) The liquid) diluted to be mixed at a ratio of parts by mass) was subjected to shower development at 30 ° C. for 60 seconds with a flat nozzle pressure of 0.1 MPa to remove the thermoplastic resin layer and the intermediate layer. Subsequently, after air was blown off on the upper surface of the glass substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.

  Thereafter, a sodium carbonate / sodium hydrogen carbonate developer (trade name: T-CD1 (manufactured by FUJIFILM Corporation)) is mixed 5 times with pure water (T-CD1 is mixed in a proportion of 1 part by mass and 4 parts by mass of pure water). ), The shower pressure was set to 0.1 MPa at 32 ° C., developed for 50 seconds, and washed with pure water.

Subsequently, using a surfactant-containing cleaning solution (trade name: T-SD3 (manufactured by Fuji Film Co., Ltd.) diluted 10-fold with pure water) at 33 ° C. for 20 seconds, cone-type nozzle pressure of 0.1 MPa The residue was removed by rubbing the formed pattern image with a rotating brush having soft nylon hairs. Furthermore, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, thereby obtaining a desired black pattern. The outline of the black pattern A for pattern omission evaluation having a pattern outer periphery of 400 mm, a pattern inner periphery of 280 mm, and a pattern area of 51 cm ² obtained when the mask A is used is shown in FIG.
The obtained black pattern A was evaluated as follows.

(1) Black pattern missing in outer peripheral portion of substrate Black plate with transmission density of 5.0 is cut out to the size of black pattern A (hereinafter referred to as substrate) having the structure shown in FIG. The board was inserted in the part where the board was cut out. Next, the pattern non-formed part 27 in FIG. 12 in the produced substrate surface was shielded with black paper. In this state, observation with transmitted light was performed along the outer peripheral portion 21 ′ of the substrate prepared with an optical microscope (manufactured by Olympus; MX50), and the pattern missing of the black pattern A (hereinafter also referred to as pattern defect) was examined. .

(1-1) Frequency of pattern loss The number of pattern loss was divided by the observed peripheral distance of the substrate of 400 mm to obtain the frequency of pattern defects per 1 cm. The smaller the value, the less likely the defect will occur.
The practical level is C or higher.
(Evaluation criteria)
A; 0 pieces B: 1 to 2 pieces C: 3 to 5 pieces D; 6 to 10 pieces E; 11 pieces or more

(1-2) Size of Defect Part The size of the pattern missing part (how much missing from the outer peripheral part 21 ′ of the substrate to the inside of the substrate) was measured. The smaller the value, the smaller the defect and the harder it is to visually recognize the defective part.
The practical level is C or higher.
(Evaluation criteria)
A: 20 μm or less B: Larger than 20 μm and 50 μm or smaller C: Larger than 50 μm and 100 μm or smaller D: Larger than 100 μm and 300 μm or smaller E: Over 300 μm

(2) Black pattern missing in pattern end face in substrate surface Black plate having transmission density of 5.0 is cut out to the size of black pattern A (substrate) having the structure shown in FIG. The board was inserted in the part where the board was cut out. Next, the pattern non-formation portion 27 in the prepared substrate surface was accurately measured and shielded with black paper so as to cover the border just inside the black pattern 26. In this state, observation with transmitted light was performed along the inner end face of the in-plane black pattern 26 created by an optical microscope (manufactured by Olympus; MX50), and pattern omission was examined.

(2-1) Frequency of pattern loss The number of defects was divided by the inner peripheral distance 280 mm of the observed black pattern 26 in the substrate surface to obtain the defect frequency per 1 cm. The smaller the value, the less likely the defect will occur.
The practical level is C or higher.
(Evaluation criteria)
A; 0 pieces B: 1 to 2 pieces C: 3 to 5 pieces D; 6 to 10 pieces E; 11 pieces or more

(2-2) Size of defective part The size of the missing part (how much the missing part from the inner peripheral edge of the black pattern 26 in the substrate surface to the inside of the pattern) was measured. The smaller the value, the smaller the defect and the harder it is to visually recognize the defective part.
The practical level is C or higher.
(Evaluation criteria)
A: 20 μm or less B: Larger than 20 μm and 50 μm or smaller C: Larger than 50 μm and 100 μm or smaller D: Larger than 100 μm and 300 μm or smaller E: Over 300 μm

(3) Pinhole defects in the formed black pattern The entire black pattern 26 created using the mask A in the same manner as in (2) is observed with an optical microscope (manufactured by Olympus; MX50), and pinhole defects are observed. I investigated.

(3-1) Frequency of pinhole defects The number of pinhole defects was divided by the observed pattern area 51 cm ² to obtain the defect frequency per 1 cm ² . The smaller the value, the less likely the defect will occur.
The practical level is C or higher.
(Evaluation criteria)
A; 0 pieces B: 1 to 2 pieces C: 3 to 5 pieces D; 6 to 10 pieces E; 11 pieces or more

(3-2) Size of Defect Part The circle approximate diameter of the pinhole missing part is calculated using an image analysis apparatus, and 10 (in the case of 10 or less, the number of occurrences) circle approximate diameters (unit: The average value of μm) was calculated. The smaller the value, the smaller the defect and the harder it is to visually recognize the defective part.
The practical level is C or higher.
(Evaluation criteria)
A: 20 μm or less B: Larger than 20 μm and 50 μm or smaller C: Larger than 50 μm and 100 μm or smaller D: Larger than 100 μm and 300 μm or smaller E: Over 300 μm

<Adhesion evaluation using black pattern B>
(Manufacture of black pattern B)
For the pattern missing evaluation described above, except that eight types of mask B, which is a quartz exposure mask having the mask pattern shown in FIG. The black pattern B was manufactured in the same manner as the black pattern A. Mask B is for adhesion evaluation. In the light transmission pattern portion 24 of FIG. 13, the light shielding portion is not shown, but the mask pattern shown in FIG. 10 is formed. Specifically, the light transmissive pattern portion 24 has eight types of masks B each having a size of 1 mm (1000 μm) in both vertical and horizontal directions, and the gap between the light shielding portions 23 is 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, The same thing except having arrange | positioned so that it may be set to 70 micrometers and 80 micrometers.
The outline of eight types of black patterns B having a pattern outer periphery of 400 mm and a pattern area of 100 cm ² is shown in FIG.
The following evaluation was performed using the obtained eight types of black patterns B.

(4) Adhesion of formed black pattern (4-1) Fine line adhesion of formed black pattern Eight kinds of black patterns 26 having the structure shown in FIG. B1 to B8 (each 10 mm in both vertical and horizontal directions) were observed with an optical microscope (manufactured by Olympus; MX50) to check for missing fine patterns. The size of the gap between the light shielding portions 23 of the mask B) was used as an adhesion index. The smaller the value, the better the adhesion of the fine pattern, which is suitable for creating a logo mark or the like in the pattern.
The practical level is A to E, preferably A to D, more preferably A or B.
(Evaluation criteria)
A: 10 μm fine line pattern is not missing B: 20 μm fine line pattern is not missing C: 30 μm fine line pattern is not missing D; 40 μm fine line pattern is not missing E; 50 μm fine line pattern is not missing F; 60 μm fine line No missing pattern G; No 70 μm fine line pattern missing H; No 80 μm fine line pattern missing

(4-2) Cross-cut adhesion of the formed black pattern B11 to B15 portions of the pattern created using the mask B in which the size of the gap between the light shielding portions 23 is 30 μm among the eight types of masks B ( A cross-cut test based on the JIS-K5400 method was performed in the range of 20 mm in both length and width. The five points were converted into evaluation points based on JIS-K5400, and the average points were obtained. The higher the value, the better the adhesion, and the better the process suitability after pattern formation and the mechanical strength of the pattern forming substrate.
The practical level is C or higher.
(Evaluation criteria)
A: No peeling is observed B: Although peeling is observed, it is 1% or less C: Peeling is more than 1% and 3% or less D: Peeling is more than 3% and 5% or less E; More than 5% peeling

  The evaluation results of (1) to (4) above are shown in Table 1 below.

[Example 2]
The alkali treatment performed in Example 1 was retained for 10 seconds under the steam far infrared heater heated to 110 ° C., but was retained for 10 seconds under the steam far infrared heater heated to 90 ° C. A laminate having the photocurable resin layer produced by the production method of Example 2 was produced in the same manner as in Example 1 except that.
Then, the black pattern A and the black pattern B were obtained like Example 1 except having used the laminated body which has the photocurable resin layer of Example 2. FIG. Evaluation similar to Example 1 was performed using the obtained black pattern A and black pattern B. The results are shown in Table 1 below.

[Example 3]
In Example 1, instead of a flexible film (cellulose acylate film) CAF-1 having a thickness of 80 μm, a flexible film (biaxially stretched polyethylene terephthalate film) PET-1 having a thickness of 75 μm was used. In the same manner as in Example 1, a laminate having a photocurable resin layer produced by the production method of Example 3 was produced.

  Then, the black pattern A and the black pattern B were obtained like Example 1 except having used the laminated body which has a photocurable resin layer of Example 3. FIG. Evaluation similar to Example 1 was performed using the obtained black pattern A and black pattern B. The results are shown in Table 1 below.

[Comparative Example 1]
A laminate having a photocurable resin layer produced by the production method of Comparative Example 1 was produced in the same manner as in Example 1 except that the flexible film CAF-1 was used without being subjected to alkali treatment.
Then, the black pattern A and the black pattern B were obtained like Example 1 except having used the laminated body which has the photocurable resin layer of the comparative example 1. FIG. Evaluation similar to Example 1 was performed using the obtained black pattern A and black pattern B. The results are shown in Table 1 below.

[Comparative Example 2]
Silane coupling solution (N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.3 mass% aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) on flexible film CAF-1. Was sprayed for 20 seconds in a shower and washed with pure water. A laminate having a photocurable resin layer produced by the production method of Comparative Example 2 was produced in the same manner as in Example 1 except that this was heated with a preheating device.
Then, the black pattern A and the black pattern B were obtained like Example 1 except having used the laminated body which has the photocurable resin layer of the comparative example 2. FIG. Evaluation similar to Example 1 was performed using the obtained black pattern A and black pattern B. The results are shown in Table 1 below.

  From Table 1 above, the black pattern obtained by exposing the laminate having the photocurable resin layer produced by the production method of the present invention has a substrate end defect, a pattern end defect in the substrate, and a pinhole in the pattern. It was found that the adhesion was excellent.

[Examples 101 to 103, Comparative Examples 101 and 102]
<Manufacturing and Evaluation of Capacitive Input Device>
1st and 2nd of the structure of FIG. 1A which formed one each in X sensor which is the 1st transparent electrode pattern 3, and Y sensor which is the 2nd transparent electrode pattern 4 on both surfaces of glass 1 ', respectively. A black pattern obtained by using the mask A in each Example and Comparative Example using the highly transparent adhesive layer 14 on the substrate having the transparent electrode pattern (in FIG. 1A, the flexible support 1 and the black pattern (Corresponding to a laminated body of a certain mask layer 2) and a cover glass 13 were further bonded to produce a capacitance type input device of each example and comparative example. The produced capacitive input devices of the examples and comparative examples were bonded to the LCD module to obtain image display devices of the examples and comparative examples.
It has been found that the image display device produced using the black pattern produced by the method for producing a laminate having the photocurable resin layer of the present invention has no defects and is excellent in display characteristics. On the other hand, the image display device produced using the produced black pattern shown in the comparative example has a poor display quality because there are many defects in the frame part and the defective part can be visually recognized.

1 Flexible support 1 'Front plate (glass)
2 Mask Layer 3 First Transparent Electrode Pattern 3a Pad Part 3b Connection Part 4 Second Transparent Electrode Pattern 5 Insulating Layer 6 Conductive Element 7 Transparent Protective Layer 8 Opening 10 Capacitive Input Device 11 Tempered Glass 12 Conductive element 13 Cover glass 14 Transparent adhesive layer 21 Arrangement position 21 ′ of laminate (work) having photocurable resin layer of substrate (flexible support in laminate having photocurable resin layer) Outer peripheral portion 22 Mask outer periphery 23 Mask light shielding portion 24 Light transmission pattern portion (region where black pattern is formed)
25 Mask 26 Black pattern (a layer formed by curing a photocurable resin layer in a laminate having a photocurable resin layer)
27 Pattern non-formation part

Claims (12)

A step of alkali-treating at least one surface of the flexible support;
Overlaying the photocurable resin layer of a photosensitive film having a photocurable resin layer on a temporary support on the alkali-treated surface of the flexible support, and press-bonding;
Only including,
The photocurable resin layer contains a carboxylic acid group-containing resin,
The method for producing a laminate having a photocurable resin layer, wherein the flexible support is a cellulose-based support or a polyester-based support .   The said photosensitive film has at least the said temporary support body, a thermoplastic resin layer, and the said photocurable resin layer in this order, Manufacture of the laminated body which has a photocurable resin layer of Claim 1 characterized by the above-mentioned. Method. The method for producing a laminate having a photocurable resin layer according to claim 1 or 2 , wherein the crimping step is performed while heating. The said photocurable resin layer contains at least one among a black colorant and a white colorant, The manufacture of the laminated body which has a photocurable resin layer as described in any one of Claims 1-3 characterized by the above-mentioned. Method. Look containing a cured product laminate to have a photocurable resin layer on at least one surface of a flexible support,
When exposure is performed using a mask pattern in which the size of the gap between the light shielding portions is 50 μm, the number of pattern defects of the photocurable resin layer on the pattern end surface of the flexible support is 5 or less per cm. ,
3% or less of peeling of the photocurable resin layer after carrying out a cross-cut test based on the JIS-K5400 method when exposed using a mask pattern arranged with a gap of 30 μm between the light shielding portions And
The photocurable resin layer contains a carboxylic acid group-containing resin,
The electrostatic capacity type input device, wherein the flexible support is a cellulose support or a polyester support . 6. The capacitive input device according to claim 5 , further comprising a mask layer, wherein at least one layer of the cured product laminate is the mask layer. The electrostatic capacitance-type input according to claim 5 or 6 , comprising the following elements (1) to (5), wherein at least one layer of the cured product laminate is the (1) mask layer. apparatus.
(1) Mask layer (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (3) The first transparent electrode pattern and the electric A plurality of second transparent electrode patterns comprising a plurality of pad portions that are electrically insulated and extend in a direction intersecting the first direction (4) The first transparent electrode pattern and the second An insulating layer that electrically insulates the transparent electrode pattern (5) electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern, and the first transparent electrode pattern and the second transparent electrode pattern Conductive element separate from the second transparent electrode pattern It includes the process of exposing the laminated body which has a photocurable resin layer manufactured with the manufacturing method of the laminated body which has a photocurable resin layer as described in any one of Claims 1-4. A method for manufacturing a capacitive input device. The method for manufacturing a capacitive input device according to claim 8 , wherein patterning exposure is performed on the laminate having the photocurable resin layer. A method for producing a capacitance type input devices having a mask layer, static according to claim 8 or 9, characterized in that to form the mask layer by exposing the laminate having the photocurable resin layer A method for manufacturing a capacitive input device. It is a manufacturing method of the capacitance-type input device which has an element of following (1)-(5), and exposes the laminated body which has the said photocurable resin layer, The said (1) mask layer is formed. The method for manufacturing a capacitive input device according to any one of claims 8 to 10 .
(1) Mask layer (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (3) The first transparent electrode pattern and the electric A plurality of second transparent electrode patterns comprising a plurality of pad portions that are electrically insulated and extend in a direction intersecting the first direction (4) The first transparent electrode pattern and the second An insulating layer that electrically insulates the transparent electrode pattern (5) electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern, and the first transparent electrode pattern and the second transparent electrode pattern Conductive element separate from the second transparent electrode pattern An image display device having as a component a capacitive input device according to any one of claims 5-7.

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