WO2014112429A1

WO2014112429A1 - Heat-resistant decorating coloring composition, method for producing electrostatic capacitance type input device, and electrostatic capacitance type input device, as well as image display device provided with same

Info

Publication number: WO2014112429A1
Application number: PCT/JP2014/050276
Authority: WO
Inventors: 後藤　英範; 隆志有冨
Original assignee: 富士フイルム株式会社
Priority date: 2013-01-15
Filing date: 2014-01-10
Publication date: 2014-07-24
Also published as: CN104903409A; CN104903409B; JP2014137617A; JP5860419B2

Abstract

A heat-resistant decorating coloring composition is characterized in containing at least a white inorganic pigment (A) and silicone-based resin (B). A method for producing an electrostatic capacitance type input device is a method for producing an electrostatic capacitance type input device that includes a front plate and at least the following elements provided on one of surfaces of the front plate: (1) a decorating layer; (3) a plurality of first transparent electrode patterns formed with a plurality of pad portions extending in a first direction via connection portions; (4) a plurality of second electrode patterns that are electrically insulated from the first transparent electrode patterns and that are composed of a plurality of pad portions that extend in a direction crossing the first direction; (5) an insulating layer that electrically insulates the first transparent electrode patterns and the second electrode patterns from one another, the method being characterized in including the step of forming at least (1) the decorating layer by applying the heat-resistant decorating coloring composition to the one of surfaces of the front plate.

Description

Heat resistant decorative coloring composition, method of manufacturing capacitance type input device, capacitance type input device, and image display device provided with the same

The present invention relates to a heat-resistant decorative coloring composition for producing a capacitance-type input device capable of detecting a contact position of a finger as a change in capacitance, a method for producing a capacitance-type input device, and The present invention relates to a capacitance-type input device obtained by a manufacturing method, and an image display device including the capacitance-type input device as a component.

In recent years, in electronic devices such as mobile phones, car navigation systems, personal computers, ticket vending machines, and terminals of banks, a tablet-type input device is disposed on the surface of a liquid crystal device or the like, and an instruction image displayed in the image display area of the liquid crystal device There are some which can input information corresponding to an instruction image by touching a finger, a touch pen or the like to a portion where the instruction image is displayed while referring to FIG.

Such an input device (touch panel) includes a resistive film type, a capacitance type, and the like. However, the resistive film type input device has a drawback that it has a narrow operating temperature range and is weak to change with time because it has a two-sheet structure of film and glass and presses the film to make it short.

On the other hand, the capacitance-type input device has an advantage that it is sufficient to form the translucent conductive film on only one substrate. In such an electrostatic capacitance type input device, for example, an electrode pattern is extended in a direction crossing each other, and when a finger or the like comes in contact, a change in electrostatic capacitance between the electrodes is detected to detect an input position. There is a capacitive input device of the type described below (for example, see 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, and a weak current flowing when a finger is in contact or in proximity is formed. There is also a capacitive input device of a type that detects an input position. As such an electrostatic capacitance type input device, a plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction through the connection portion and the first transparent electrode pattern Capacitance type comprising a plurality of second transparent electrode patterns comprising a plurality of pad portions electrically insulated from each other via an interlayer insulating layer and extending in a direction intersecting the first direction An input device is disclosed (see, for example, Patent Document 2 below). However, the capacitive input device has a problem that the capacitive input device becomes thick and heavy because the front plate is stacked on the manufactured capacitive input device.

Furthermore, a capacitive touch panel in which a mask layer, a sense circuit, and an interlayer insulating layer are integrally formed on the surface on one side of the front plate is disclosed (for example, see Patent Document 3 below). In the capacitive touch panel described in Patent Document 3, since the front plate is integrated with the capacitive input device, thinning and weight reduction become possible, and furthermore, the mask circuit hides the sense circuit. Improves the appearance of the device.

Unexamined-Japanese-Patent No. 2007-122326 Patent No. 4506785 JP, 2009-193587, A JP 2011-218561 A JP 2008-169237 A

Patent Document 3 only described that the mask layer may be formed by a black resin or other opaque coating material, but if necessary, various color tones (between the mask layer and the front plate) A decorative layer of black, white, pastel color, metallic, etc.) can be provided, and in recent years, it is required to increase the lightness and whiteness of the white decorative layer particularly among them.
As a method of providing this decoration layer, the thing by liquid resist application, screen printing, etc. is the mainstream conventionally.

On the other hand, smartphones and tablet PCs equipped with a capacitive touch panel on a liquid crystal or organic EL display have been developed using tempered glass represented by Goringa glass of Corning as the front plate (surface directly in contact with a finger) , Has been announced.
As a result of investigations by the present inventors, when a white decorative layer is to be formed on this reinforced glass substrate using a liquid resist for forming a decorative layer or a screen printing ink, a liquid resist having a small hiding power or a screen printing ink is used. In order to form a white decorative layer by using it, it is necessary to perform liquid resist application and screen printing in several times, and due to this, bubbles, unevenness occur and the yield is reduced due to a large number of processes, etc. It turned out that there is a problem that cost reduction is not easy. Furthermore, after forming a decoration layer on tempered glass, when heated at the process of producing circuits, such as a transparent conductive layer, there existed a problem that whiteness falls.

On the other hand, as a white film having high heat resistance, a white thermosetting resin composition containing at least (A) thermosetting resin substantially not containing silicon in the molecule, and (B) white coloring agent A multilayer film is proposed which is characterized in that the following layer is provided on at least one side of a polyimide film (see, for example, Patent Document 4). However, the multilayer film described in Patent Document 4 also has a problem in that whiteness decreases when it is heated to a high temperature in the process of producing a circuit such as a transparent conductive layer.

Similarly, a white polyimide film obtained by imidizing a polyimide precursor film in which a white pigment is mixed with a polyamic acid obtained by reacting a diamine and an aromatic tetracarboxylic acid as a film having high heat resistance is proposed. (See, for example, Patent Document 5). However, the white polyimide film described in Patent Document 5 similarly has a problem that whiteness is lowered when heated at a high temperature in the process of producing a circuit such as a transparent conductive layer.

As mentioned above, when the present inventors examined and a white decorative layer was formed by the method as described in these documents, all the characteristics of the lightness after transfer, whiteness, reticulation, and adhesiveness were satisfied. It turned out that the thing of the performance which can not be obtained can not be obtained. Moreover, it turned out that it is also difficult to obtain a white decorative layer satisfying the above characteristics at a high yield.
The problem to be solved by the present invention is to provide a heat resistant decorative coloring composition which can obtain a white decorative layer having good lightness, whiteness, reticulation and adhesion at a high yield. It is.
At the same time, a capacitive input device capable of thinning and reducing the weight using the coloring composition for heat-resistant decoration satisfying the above characteristics can be manufactured in high quality in a simple process. A manufacturing method of a capacitance type input device, a capacitance type input device obtained by the manufacturing method, and an image display device using the capacitance type input device.

On the other hand, as a result of repeating examination further about the whiteness of a white decorative layer as a result of the present inventors, after forming a white decorative layer, when forming a transparent electrode pattern which consists of ITO etc., heating at high temperature As necessary, it has been found that the decrease in whiteness of the white decorative layer is remarkable during high temperature heating. Therefore, it has been found that a white decorative layer having good lightness, whiteness, reticulation and adhesion can be obtained at a high yield by using a silicone-based resin as a coloring composition for heat-resistant decoration. The present invention has been achieved.

The present invention, which is a specific means for solving the above problems, is as follows.
[1] A coloring composition for heat resistant decoration, characterized by comprising at least (A) a white inorganic pigment and (B) a silicone resin.
[2] It is preferable that the coloring composition for heat-resistant decoration as described in [1] further contains (C) antioxidant.
[3] In the coloring composition for heat-resistant decoration as described in [1] or [2], (B) the silicone resin is represented by at least the following general formula (1) in a modified silicone resin or in a molecule: It is preferable to include a straight silicone resin containing a siloxane structure.

In the general formula (1), R ¹ independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear or branched chain having 1 to 20 carbon atoms Or a cyclic alkyl group, a linear, branched or cyclic substituted alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms Represents a group or an aralkyl group having 7 to 20 carbon atoms.
[4] The coloring composition for heat-resistant decoration as described in [3] is, in the general formula (1), R ¹ independently represents a hydrogen atom, a linear, branched or cyclic C ¹ to C 20 carbon atom. It is preferable to represent the following alkyl group, a linear, branched or cyclic substituted alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 9 carbon atoms.
[5] In the coloring composition for heat-resistant decoration as described in [3] or [4], in general formula (1), R ¹ preferably independently represents a hydrogen atom, a methyl group or a tolyl group .
[6] The heat-resistant and decorative colored composition according to any one of [1] to [5], wherein the content ratio of the white inorganic pigment to the total solid content of the heat-resistant and decorative colored composition is from 20 to It is preferable that it is 75 mass%.
[7] In the heat-resistant and decorative coloring composition according to any one of the above [1] to [6], the white inorganic pigment is preferably rutile type titanium oxide surface-treated with an inorganic substance.
[8] The heat-resistant decorative coloring composition according to [7] is that the rutile-type titanium oxide surface-treated with an inorganic substance is rutile-type titanium oxide surface-treated with at least one of alumina and zirconia. Is preferred.
[9] The heat-resistant and decorative coloring composition according to any one of [1] to [8], wherein the heat-resistant and decorative coloring composition is used to decorate a capacitive input device front plate. Is preferred.
[10] A method of manufacturing a capacitive input device having a front plate and at least one of the following elements (1) and (3) to (5) on one of the surfaces of the front plate, And [9] to form at least (1) a decorative layer by applying the coloring composition for heat-resistant decoration according to any one of the above [9] to one side of a front plate. Of manufacturing a capacitive input device.
(1) Decorative layer (3) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction through connection portions (4) A first transparent electrode pattern and electricity And a plurality of second electrode patterns (5) consisting of a plurality of pad portions formed to extend in a direction intersecting the first direction, and the first transparent electrode pattern and the second electrode pattern In the method of manufacturing the capacitance-type input device according to the insulating layer [11] [10] for electrically insulating the electrodes, the capacitance-type input device further includes (6) a first transparent electrode pattern and a second It is preferable to electrically connect to at least one of the electrode patterns and to have a conductive element different from the first transparent electrode pattern and the second electrode pattern.
[12] In the method of manufacturing a capacitance-type input device according to [10] or [11], the second electrode pattern is preferably a transparent electrode pattern.
[13] In the method of manufacturing a capacitance-type input device according to any one of [10] to [12], (1) the thickness of the decorative layer is preferably 1 to 40 μm.
[14] The method for producing a capacitance-type input device according to any one of [10] to [13], wherein the heat resistant decorative coloring composition is applied to one side of the surface of the front plate After that, it is preferable to heat at 180 to 300 ° C. under an environment of 0.08 to 1.2 atm to form (1) a decorative layer.
[15] In the method of manufacturing a capacitance-type input device according to [14], the heating is preferably performed in an air environment.
[16] The method for producing a capacitance-type input device according to any one of [10] to [15], the application of the coloring composition for heat-resistant decoration to one surface of a front plate Preferably, the heat resistant decorative coloring composition is printed.
[17] The method of manufacturing a capacitance-type input device according to any one of [10] to [16], (1) of the surface of the decorative layer on the side opposite to the surface facing the front plate It is preferable to further form (2) a mask layer on the surface.
[18] [17] The method of manufacturing a capacitance-type input device according to [18] includes at least one of (3) a first transparent electrode pattern and (4) a second electrode pattern, one surface of a front plate and (2) Preferably, the mask layer is disposed across the two areas of the surface opposite to the surface facing the front plate among the surfaces of the mask layer.
[19] In the method of manufacturing a capacitance-type input device according to [17] or [18], the capacitance-type input device further includes: (6) the first transparent electrode pattern and the second electrode The first transparent electrode pattern and the second electrode pattern are electrically connected to at least one of the patterns, and (2) on the surface of the mask layer on the side opposite to the surface facing the front plate. It is preferred to have at least (6) another conductive element.
[20] The method of manufacturing a capacitance-type input device according to any one of [10] to [19] further includes all or part of the elements of (1) and (3) to (5). It is preferable to form a transparent protective layer so as to cover it.
[21] In the method of manufacturing a capacitance-type input device according to [20], the transparent protective layer is preferably formed using a curable resin composition.
[22] In the method of manufacturing a capacitive input device according to any one of [10] to [21], the capacitive input device further includes (6) a first transparent electrode pattern and a second transparent electrode pattern. Electrically connected to at least one of the first electrode pattern and having a conductive element different from the first transparent electrode pattern and the second electrode pattern, and (4) the second electrode pattern is a transparent electrode pattern , (3) the first transparent electrode pattern, (4) the second electrode pattern and (6) another conductive element, the transparent conductive material is etched using the etching pattern formed by the curable resin composition It is preferable to form by doing.
[23] In the method of manufacturing a capacitive input device according to any one of [10] to [21], the capacitive input device further comprises (6) a first transparent electrode pattern and a second transparent electrode pattern. Electrically connected to at least one of the first electrode pattern and having a conductive element different from the first transparent electrode pattern and the second electrode pattern, and (4) the second electrode pattern is a transparent electrode pattern Preferably, at least one of (3) the first transparent electrode pattern, the second transparent electrode pattern, and (6) the conductive element is formed using a conductive curable resin composition.
[24] In the method of manufacturing a capacitance-type input device according to any one of [10] to [23], one surface of the front plate is subjected to surface treatment to perform surface treatment on the front plate It is preferable to apply the curable resin composition on the surface of
[25] In the method of manufacturing a capacitive input device according to [24], it is preferable to use a silane compound for the surface treatment of the front plate.
[26] In the method of manufacturing a capacitive input device according to any one of [10] to [25], it is preferable that the front plate has an opening at least in part.
[27] A capacitance type input device manufactured by the method of manufacturing a capacitance type input device according to any one of [10] to [26].
[28] An image display apparatus comprising the capacitive input device according to [27] as a component.

According to the present invention, it is possible to provide a heat resistant decorative coloring composition capable of obtaining a white decorative layer having good lightness, whiteness, reticulation and adhesion at a high yield.
According to the present invention, in addition to this, a capacitive input device capable of thinning and reducing weight using the coloring composition for heat-resistant decoration satisfying the above-mentioned characteristics is manufactured with high quality in a simple process. Provided are a manufacturing method of a capacitance type input device that can be made possible, a capacitance type input device obtained by the manufacturing method, and an image display device using the capacitance type input device. Can.

It is sectional drawing which shows the structure of the electrostatic capacitance type input device of this invention. It is an explanatory view showing an example of a front board in the present invention. 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 processing glass in which the opening part was formed. It is a top view which shows an example of the front plate in which the decoration layer and the mask layer were 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 of a dirt prevention board. It is the schematic of the antifouling plug.

The heat resistant decorative coloring composition, the method for producing a capacitance type input device, the capacitance type input device, and the image display device according to the present invention will be described below.
Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments. In the present specification, “to” is used in the meaning including the numerical values described before and after it as the lower limit value and the upper limit value.

[Coloring composition for heat resistant decoration]
The coloring composition for heat-resistant decoration of the present invention is characterized by containing at least (A) a white inorganic pigment and (B) a silicone resin.

-(A) White inorganic pigment-
As the (A) white inorganic pigment, white pigments described in paragraph 0019 of JP-A-2009-191118 and paragraph 0109 of JP-A-2000-175718 can be used.
Specifically, in the present invention, as the white inorganic pigment, titanium oxide (rutile type), titanium oxide (anatase type), zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, barium sulfate, etc. Preferably, titanium oxide (rutile type), titanium oxide (anatase type) and zinc oxide are more preferable, titanium oxide (rutile type) and titanium oxide (anatase type) are more preferable, and rutile type titanium oxide is still more preferable.

Specific examples of titanium dioxide include JR, JRNC, JR-301, 403, 405, 600A, 605, 600E, 603, 701, 800, 805, 806, JA-1, C, 3, 4, 5, MT- 01, 02, 03, 04, 05, 100 AQ, 100 SAK, 100 SAS, 100 TV, 100 TV, 100 ZR, 150 W, 500 W, 500 H, 500 SA, 500 SAK, 500 SAS, 500 S, SMT-100 SAM, 100 SAS, 500 SAM, 500 SAS (Taika Corporation) Made, CR-50, 50-2, 57, 58, 58-2, 60, 60-2, 63, 67, 80, 85, 90, 90-2, 93, 95, 97, 953, Super 70, PC -3, PF-690, 691, 711, 736, 737, 739, 740, 42, R-550, 580, 630, 670, 680, 780, 780-2, 820, 830, 850, 855, 930, 980, S-305, UT 771, TTO-51 (A), 51 (C), 55 (A), 55 (B), 55 (C), 55 (D), S-1, S-2, S-3, S-4, V-3, V-4, MPT-136, FTL- 100, 110, 200, 300 (manufactured by Ishihara Sangyo Co., Ltd.), KA-10, 15, 20, 30, KR-310, 380, KV-200, STT-30EHJ, 65C-S, 455, 485SA15, 495M, 495MC ( Titanium industry, TA-100, 200, 300, 400, 500, TR-600, 700, 750, 840, 900 (manufactured by Fuji titanium industry) and the like, and these may be used alone or in combination. It may be.

In the present invention, the surface of the white inorganic pigment (especially titanium oxide) can be treated with silica, alumina, titania, zirconia, organic matter, and the like in combination.
As a result, the catalytic activity of the white inorganic pigment (particularly titanium oxide) can be suppressed, and the heat resistance, the fluorescence and the like can be improved.
From the viewpoint of the whiteness of the decorative layer after heating, in the present invention, the white pigment is preferably rutile titanium oxide surface-treated with an inorganic substance, and surface-treated with at least one of alumina treatment and zirconia treatment It is more preferable that it is rutile type titanium oxide, and it is especially preferable that it is rutile type titanium oxide surface-treated by combined treatment with alumina and zirconia.

That the content of the white inorganic pigment is 20 to 75% by mass with respect to the total solid content of the heat-resistant decorative coloring composition has good brightness and whiteness, and simultaneously satisfies other required characteristics It is preferable from the viewpoint of forming a decoration layer. Moreover, when using the coloring composition for heat-resistant decoration of this invention for the manufacturing method of the electrostatic capacitance type input device of this invention mentioned later, also from a viewpoint of fully reducing development time, the total solid of the said decoration layer It is preferable that the content ratio of the above-mentioned white inorganic pigment to 20 minutes is 20 to 75% by mass.
The content ratio of the white inorganic pigment to the total solid content of the heat-resistant decorative coloring composition is more preferably 25 to 60% by mass, and still more preferably 30 to 50% by mass.
The total solid content as used in this specification means the total mass of the non-volatile component which remove | eliminated the solvent etc. from the said coloring composition for heat-resistant decoration.

It is desirable to use the white inorganic pigment (note that the same applies to other colorants used in the mask layer described later) as a dispersion. The dispersion can be prepared by adding and dispersing a composition obtained by mixing the white inorganic pigment and the pigment dispersant in advance to an organic solvent (or vehicle) described later. The above-mentioned vehicle refers to the part of the medium in which the pigment is dispersed when the paint is in a liquid state, and it is liquid and dissolves and dilutes a component (binder) which combines with the pigment to form a coating film. And a component (organic solvent).

The disperser used to disperse the white inorganic pigment is not particularly limited, and is described, for example, in "Encyclopedia of Pigments", First Edition, Asakura Shoten, 2000, p. Well-known dispersers, such as a kneader, a roll mill, an atlider, a super mill, a dissolver, a homomixer, a sand mill etc. are mentioned. Furthermore, the mechanical grinding described on page 310 of the document may be used to pulverize using frictional force.

From the viewpoint of dispersion stability and hiding power, the white inorganic pigment as the white inorganic pigment used in the present invention is preferably a white inorganic pigment having an average particle diameter of primary particles of 0.16 μm to 0.3 μm, and further preferably 0.18 μm. White inorganic pigments of ̃0.27 μm are preferred. Furthermore, white inorganic pigments of 0.19 μm to 0.25 μm are particularly preferred. If the average particle size of the primary particles is smaller than 0.16 μm, the hiding power may be rapidly reduced to make the base of the mask layer more visible or to cause an increase in viscosity. On the other hand, if it exceeds 0.3 μm, the whiteness may be reduced and the hiding power may be rapidly reduced, and the surface condition may be deteriorated upon application.
The term "average particle size of primary particles" as used herein refers to the diameter when the electron micrograph image of the particles is a circle of the same area, and "number average particle size" refers to the above-mentioned particles for a large number of particles. The diameter is determined, and the average value of 100 arbitrarily selected particle sizes among them is said.
On the other hand, when measuring by the average particle diameter in a dispersion liquid and a coating liquid, laser scattering HORIBA H (made by Horiba advanced techno company) can be used.

-(B) Silicone resin-
A well-known thing can be used as said silicone resin.
A silicone resin is obtained by partially denatured resin with the following silane compound, dehydrating condensation of a modified silicone resin to which various properties are given, and a silane compound having an alkoxy group or silanol group, and utilizing the intrinsic property of silicone It can be classified as straight silicone. In the coloring composition for heat-resistant decoration of the present invention, the silicone-based resin contains a modified silicone resin or a straight silicone resin containing at least a siloxane structure represented by the following general formula (1) in the molecule. Is preferred.
Acrylic resin modified silicone resin (KR-9706 manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by polymerizing or copolymerizing monomers obtained by reacting a silane compound with acrylic monomers such as acrylic acid (KR-9706 manufactured by Shin-Etsu Chemical Co., Ltd.) as modified silicone resin Polyester resin-modified silicone resin in which a silane compound is reacted with hydroxyl group of epoxy resin, epoxy resin-modified silicone resin in which epoxy-containing silane compound is reacted with amino group residue of resin, alkyd resin in which alkyd resin is modified with reactive silane compound A modified silicone resin, a rubber silicone resin which directly forms a covalent bond with a resin using an oxime initiator, and the like can be used.

As the straight silicone, one having at least a siloxane structure represented by the following general formula (1) in a molecule can be used.

In the general formula (1), R ¹ independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear or branched chain having 1 to 20 carbon atoms Or a cyclic alkyl group, a linear, branched or cyclic substituted alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms It is a group or an aralkyl group having 7 to 20 carbon atoms, and a plurality of R ^{1 s} may be the same or different. That is, the straight silicone having a siloxane structure represented by the general formula (1) may be a condensate of the same siloxane structure or a co-condensate of different combinations.

The halogen atom represented by R ^1, a fluorine atom include chlorine atom.
Examples of the linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms represented by R ¹ include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group and an i-butoxy group. And sec-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy, cyclopentyloxy, cyclohexyloxy and the like.
The linear, branched or cyclic alkyl group having 1 to 20 carbon atoms represented by R ¹ is, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group Groups, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like.
Among the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms represented by R ¹ , an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
In addition, as the linear, branched or cyclic substituted alkyl group having 1 to 20 carbon atoms represented by R ¹ , examples thereof include an arylalkyl group, a fluoroalkyl group, a chloroalkyl group, a hydroxyalkyl group, and (meth) acryloxyalkyl Groups and mercaptoalkyl groups can be mentioned. Specific examples thereof include, for example, phenylmethyl (benzyl) group, diphenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-n-propyl group, 2-phenyl-2-propyl (cumyl ), 3-phenyl-n-propyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl, 4-phenylbutyl, 1-phenylpentyl, 2-phenylpentyl, 3-) Phenylpentyl, 4-phenylpentyl, 5-phenylpentyl, 1-phenylhexyl, 2-phenylhexyl, 3-phenylhexyl, 4-phenylhexyl, 5-phenylhexyl, 6-phenylhexyl Group, 1-phenylcyclohexyl group, 2-phenylcyclohexyl group, 3-phenylcyclohexyl group 1-phenylheptyl group, 2-phenylheptyl group, 3-phenylheptyl group, 4-phenylheptyl group, 5-phenylheptyl group, 6-phenylheptyl group, 1-phenyloctyl group, 2-phenyloctyl group, 3- Phenyloctyl group, 4-phenyloctyl group, 5-phenyloctyl group, 6-phenyloctyl group, 1-naphthylethyl group, 2-naphthylethyl group, 1-naphthyl-n-propyl group, 2-naphthyl-2-propyl group Group, 3-naphthyl-n-propyl group, 1-naphthylbutyl group, 2-naphthylbutyl group, 3-naphthylbutyl group, 4-naphthylbutyl group, 1-naphthylpentyl group, 2-naphthylpentyl group, 3-naphthyl group Pentyl group, 4-naphthylpentyl group, 5-naphthylpentyl group, 1-naphthylhexyl group, 2-naphthy Hexyl group, 3-naphthylhexyl group, 4-naphthylhexyl group, 5-naphthylhexyl group, 6-naphthylhexyl group, 1-naphthylcyclohexyl group, 2-naphthylcyclohexyl group, 3-naphthylcyclohexyl group, 1-naphthylheptyl group , 2-naphthylheptyl group, 3-naphthylheptyl group, 4-naphthylheptyl group, 5-naphthylheptyl group, 6-naphthylheptyl group, 1-naphthyloctyl group, 2-naphthyloctyl group, 3-naphthyloctyl group, 4 Arylalkyl groups such as -naphthyloctyl group, 5-naphthyloctyl group, 6-naphthyloctyl group, etc .; fluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, (trifluoromethyl) methyl group, pentafluoroethyl group , 3-fluoro-n-propyl, 2- ( Trifluoromethyl) ethyl group, (pentafluoroethyl) methyl group, heptafluoro-n-propyl group, 4-fluoro-n-butyl group, 3- (trifluoromethyl) -n-propyl group, 2- (pentafluoro) Ethyl) Ethyl group, (Heptafluoro-n-propyl) methyl group, nonafluoro-n-butyl group, 5-fluoro-n-pentyl group, 4- (trifluoromethyl) -n-butyl group, 3- (pentafluoro) Ethyl) -n-propyl group, 2- (heptafluoro-n-propyl) ethyl group, (nonafluoro-n-butyl) methyl group, perfluoro-n-pentyl group, 6-fluoro-n-hexyl group, 5- (Trifluoromethyl) -n-pentyl group, 4- (pentafluoroethyl) -n-butyl group, 3- (heptafluoro-n-propyl) -n Propyl group, 2- (nonafluoro-n-butyl) ethyl group, (perfluoro-n-pentyl) methyl group, perfluoro-n-hexyl group, 7- (trifluoromethyl) -n-heptyl group, 6- ( Pentafluoroethyl) -n-hexyl group, 5- (heptafluoro-n-propyl) -n-pentyl group, 4- (nonafluoro-n-butyl) -n-butyl group, 3- (perfluoro-n-pentyl group) ) -N-propyl group, 2- (perfluoro-n-hexyl) ethyl group, (perfluoro-n-heptyl) methyl group, perfluoro-n-octyl group, 9- (trifluoromethyl) -n-nonyl group Group, 8- (pentafluoroethyl) -n-octyl group, 7- (heptafluoro-n-propyl) -n-heptyl group, 6- (nonafluoro-n-butyl) -n-phenyl group Sil group, 5- (perfluoro-n-pentyl) -n-pentyl group, 4- (perfluoro-n-hexyl) -n-butyl group, 3- (perfluoro-n-heptyl) -n-propyl group Fluoroalkyl groups such as 2- (perfluoro-n-octyl) ethyl group, (perfluoro-n-nonyl) methyl group, perfluoro-n-decyl group, 4-fluorocyclopentyl group, 4-fluorocyclohexyl group and the like; And chloromethyl group, 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 3-chlorocyclopentyl group, 4-chlorocyclohexyl group, hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxycyclopentyl group, 4-hydroxycyclohexyl group, 3- (meth) acryloxypropyl group, 3-mercapto A propyl group etc. can be mentioned.
Further, as the linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms represented by R ¹ , for example, a vinyl group, 1-methylvinyl group, 1-propenyl group, allyl group (2-propenyl group) And 2-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 3-cyclopentenyl group, 3-cyclohexenyl group and the like. Among the linear, branched or cyclic substituted alkyl group having 1 to 20 carbon atoms represented by R ¹ , an arylalkyl group is preferable, and a cumyl group is more preferable.
The aryl group having 6 to 20 carbon atoms represented by ^{R 1,} for example, a phenyl group, o- tolyl group, m- tolyl group, p- tolyl group, 2,3-xylyl, 2,4-xylyl group And 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 1-naphthyl and the like. Among the aryl groups having 6 to 20 carbon atoms represented by R ¹ , from the viewpoint of hardly generating benzene upon heating, other than unsubstituted phenyl group, that is, o-tolyl group, m-tolyl group, p-tolyl group, 2 , 3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 1-naphthyl group is preferred, o- Tolyl group, m-tolyl group and p-tolyl group are more preferable.
Further, examples of the aralkyl group having 7 to 20 carbon atoms represented by R ¹ include a benzyl group, a phenethyl group and the like.

In the general formula (1), R ¹ independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms Is preferably a substituted alkyl group of the above or an aryl group having 6 to 9 carbon atoms (of the aryl groups, those other than unsubstituted phenyl groups are preferred from the viewpoint of hardly generating benzene upon heating); It is more preferable to represent a group or a tolyl group.
Siloxane structure represented by the general formula (1) may include a methyl group as R ^1, from the viewpoint of capable of improving particularly the L value of the decorative layer.

The straight silicone is also preferably a copolymer of a siloxane structure represented by the general formula (1) in which R ¹ is different from ^one another. In this case, the siloxane structure represented by the above general formula (1) wherein R ¹ is an alkyl group, and the siloxane structure represented by the above general formula (1) wherein R ¹ is a hydrogen atom, a substituted alkyl group or an aryl group And copolymers thereof are preferably mentioned. The copolymerization ratio is not particularly limited, but the siloxane structure represented by the general formula (1) in which R ¹ is an alkyl group is 50 to 50 among all the siloxane structures represented by the general formula (1). It is preferably 100 mol%, more preferably 60 to 100 mol%, and particularly preferably 70 to 100 mol%.

As a straight silicone used for the coloring composition for heat resistant decoration of the present invention, in addition to the siloxane structure represented by the said General formula (1) in a molecule | numerator, the siloxane structure represented by following General formula (2) Straight silicones containing a siloxane structure consisting of cocondensation with can also be preferably used.

In the general formula (2), R ² can use the same substituents as R ¹ in formula (1), is the same as R ¹ preferably ranges.

Specific examples of straight silicones include alkyl straight silicones (such as methyl straight silicones), alkyl aryl straight silicones such as methylphenyl, prepared from the condensation of a silane compound having an alkyl group having 1 to 20 carbon atoms and an alkoxy group. And aryl based straight silicones such as phenyl and hydrogen based straight silicones such as methyl hydrogen can be used.
More preferred are methyl-based straight silicone resin, methyl-tolyl-based straight silicone resin, methylphenyl-based straight silicone resin, acrylic resin-modified silicone resin, methyl-hydrogen-based straight silicone resin, and hydrodenyl-based straight silicone resin. Particularly preferred are methyl-based straight silicone resin, methyl-tolyl-based straight silicone resin, methyl-hydrogen-based straight silicone resin, and hydro-denyl-based straight silicone resin from the viewpoint of preventing benzene from being generated and suppressing the decrease in lightness.
These silicone resins may be used alone or in combination of two or more, and the film physical properties can be controlled by mixing them at an arbitrary ratio.
The generation of benzene can be quantified by gas chromatography mass spectrometry (GC-MS). The decorative layer formed by the method for producing a capacitance-type input device according to the present invention, or the decorative layer obtained by applying the coloring composition for heat resistance decoration according to the present invention is benzene as a decomposition product when heated. Is preferable, and it is more preferable not to contain benzene. The content of benzene as a decomposition product when heating the decorative layer is preferably less than 29 mg per 100 cm ^{2 of the} decorative layer, more preferably less than 19 mg, particularly preferably less than 9.2 mg Preferably, less than 0.01 mg is more particularly preferred.

The weight average molecular weight of the straight silicone is preferably 1,000 to 1,000,000, more preferably 2,000 to 800,000, and particularly preferably 2,500 to 500,000.

As a silane compound used to prepare modified silicone resin and straight silicone resin,
Tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltributoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Isobutyltrimethoxysilane, Propyltrimethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyltriethoxysilane, Vinyltrimethoxyethoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, Phenyltriacetoxysilane , Cumyltrimethoxysilane, tolyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyl Trimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxy Silane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycide Xylethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyl Pirtriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxy Propyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidone X-butyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycid X-butyl trimethoxysilane , Δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriol Methoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4- Epoxycyclohexyl) propyl tri Trialkoxy such as toxilsilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, triacyloxy or triphenoxysilanes, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropyl Methyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethyldimethoxysilane, γ-mercaptopropyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, vinylmethyl Dimethoxysilane, vinylmethyldiethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethyldiethoxysilane, α-glycidoxyethyl ester Rudimethoxysilane, α-glycidoxyethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxy Propylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ- Glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyl Methoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycid Alkoxysilanes or diacyloxysilanes such as xylpropyl phenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, dimethoxymethylsilane, trimethoxysilane, dimethylethoxysilane, diacetoxymethylsilane, diethoxymethylsilane, diethylmethylsilane Silane, triethylsilane, butyldimethylsilane, dimethylphenylsilane, methylphenylvinylsilane, diphenylmethylsilane, tripropylsilane, tripentyloxysilane, toffee Nylsilane, Trihexylsilane, Diethylsilane, Allyldimethylsilane, Methylphenylsilane, Diphenylsilane, Phenylsilane, Octylsilane, 1,4-Bis (dimethylsilyl) benzene, and 1,1,3,3-Tetramethyldisiloxane , Dimethyltolylsilane, methyltolylvinylsilane, ditolylmethylsilane, tolylylsilane, dimethylbenzylsilane, methylbenzylvinylsilane, dibenzylmethylsilane, tribenzylsilane, diphenylsilane, 2-chloroethylsilane, bis [(p-dimethyl), Silyl) phenyl] ether, 1,4-dimethyldisilylethane, 1,3,5-tris (dimethylsilyl) benzene, 1,3,5-trimethyl-1,3,5-trisilane, poly (methylsilylene) phenylene , Poly (methylsilylene) methylene, tetrachlorosilane, trichlorosilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, fluorotrichlorosilane, fluorotrichlorosilane Trimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, methyltrichlorosilane, methyltri-n-propoxysilane Silane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, 2- (trifluoromethyl) ethyl trichlorosilane, 2- (trifluoromethyl) Ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri-i-propoxysilane, 2- (trifluoro) Methyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-hexyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltrimethoxy Silane, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysilane , 2- (perfluoro-n-hexyl) Ethyl tri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyl tri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyl tri Methoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-i-propoxy Silane, 2- (perfluoro-n-octyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec-butoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrithiol Methoxysilane, hydroxide Methyltri-n-propoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltri-n-butoxysilane, hydroxymethyltri-sec-butoxysilane, 3- (meth) acryloxypropyltrichlorosilane, 3- (meth) Acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltri-i-propoxysilane, 3 -(Meth) acryloxypropyltri-n-butoxysilane, 3- (meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Liethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n-butoxysilane, 3-mercaptopropyltri-sec-butoxysilane, vinyltrichloride Chlorosilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane Allyltri-i-propoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane, phenyltrichlorosilane, phenyltri-n-propoxysilane, phenyltri- i-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, methyldichlorosilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi-i-propoxysilane, methyldi-n-butoxysilane Methyldi-sec-butoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, ( Methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n-octyl) Ethyl] diemethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-i-propoxy Silane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-sec-butoxysilane, (methyl ) (Γ-glycidoxypropyl) dichlorosilane, (methyl) (γ-glycidoxypropyl) dimethoxysilane, (methyl) (γ-glycidoxypropyl) diethoxysilane, (methyl) (γ-glycidoxy) Propyl) di-n-propoxysilane, (methyl) (γ-glycidoxypropyl) di-i-propoxysilane, (methyl) (γ-glycidoxy) Propyl) di-n-butoxysilane, (methyl) (γ-glycidoxypropyl) di-sec-butoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3-mercaptopropyl) dimethoxysilane (Methyl) (3-mercaptopropyl) diethoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) di-i-propoxysilane, (methyl) ( 3-Mercaptopropyl) di-n-butoxysilane, (methyl) (3-mercaptopropyl) di-sec-butoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (methyl) (methyl) ( Vinyl) diethoxysilane, (methyl) (vinyl) di-n-propoxysilane, Methyl) (vinyl) di-i-propoxysilane, (methyl) (vinyl) di-n-butoxysilane, (methyl) (vinyl) di-sec-butoxysilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane , Divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, Diphenyldi-i-propoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsila Bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro ) (Vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane, (ethoxy) (methyl) diphenyl A silane etc. can be mentioned, respectively. However, the present invention is not limited by these specific examples.

A commercially available thing can be used as said silicone resin, such as a modified silicone resin and straight silicone resin. For example,
KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160 AS, X-22-170 B, X-22-170 BX, X-22-170 D, X-22-170 DX, X-22-176 B, X- 22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672, X-40- 9220, X-40-9225, X-40-9226, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-40- 460M, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR-212, KR-213, KR-217, KR-220L, KR- 242A, KR-271, KR-282, KR-300, KR-400, KR-251, KR-255, KR-401N, KR-500, KR-510, KR-5206, KR-5230, KR-5235, KR-9218, KR-9706, KR-165 (above, Shin-Etsu Chemical Co., Ltd.);
SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (all available from Toray Dow Corning);
FZ3711, FZ3722 (above, Nippon Unicar Corporation);
DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS- 227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (above, Chisso);
Methyl silicate MS51, Methyl silicate MS56 (above, Mitsubishi Chemical Corporation);
Ethyl Silicate 28, Ethyl Silicate 40, Ethyl Silicate 48 (all available from Colcoat);
Partial condensation products, such as glass resin GR100, GR650, GR908, GR950 (above, Showa Denko KK) etc. are mentioned. However, the present invention is not limited by these specific examples.
Here, the heat-resistant decorative coloring composition according to the present invention is formed by applying (1) the decorative layer, the heat-resistant decorative coloring composition comprising a photocurable resin and a photopolymerization initiator is irradiated with light. It may not be cured and formed, and the coloring composition for heat-resistant decoration of the present invention may or may not contain a photocurable resin and a photopolymerization initiator. Among them, when the coloring composition for heat-resistant decoration contains an antioxidant described later, the fact that it does not contain a photopolymerization initiator can be obtained by the radical generated when exposed to a photopolymerization initiator. It is preferable from the viewpoint of sufficiently enhancing the whiteness after baking without inhibiting the function. Therefore, it is preferable that the (B) silicone resin be thermosetting.

-(C) Antioxidant-
The heat-resistant decorative coloring composition of the present invention contains an antioxidant, and the heat-resistant decorative coloring composition of the present invention is applied to one surface of a front plate of a capacitive input device described later. It is preferable from the viewpoint of raising the whiteness after baking about the obtained decorative layer after forming into a film and baking it. Here, when forming a transparent electrode pattern such as ITO in a capacitance type input device, it is necessary to bake at a high temperature, but by adding an antioxidant, the whiteness after baking may be increased. it can.
An antioxidant known as the antioxidant can be used. For example, hindered phenol type antioxidants, semi-hindered phenol type antioxidants, phosphoric acid type antioxidants, hybrid type antioxidants having phosphoric acid and hindered phenol in the molecule (phosphoric acid / hindered phenol type antioxidants Can be used.
Preferably, a phosphoric acid type antioxidant; a combination of a phosphoric acid type antioxidant and a hindered phenol type antioxidant or a semi hindered phenol type antioxidant; or a hybrid type antioxidant having phosphoric acid and a hindered phenol in the molecule It is.
A commercially available antioxidant can also be used as said antioxidant. For example, as a phosphoric acid type antioxidant, IRGAFOS168 and IRGAFOS38 (all are BASF Japan make) can be mentioned. Examples of phosphoric acid / hindered phenolic antioxidants include IRGAMOD 295 (manufactured by BASF Japan Ltd.), and as a hybrid antioxidant having phosphoric acid and hindered phenol in the molecule, Sumilyzer GP (Sumitomo Chemical Co., Ltd.) Can be mentioned.
The antioxidant is more preferably a phosphoric acid-based antioxidant from the viewpoint of preventing a decrease in whiteness, and IRGAFOS 168 is particularly preferable.
The addition amount of the antioxidant relative to the total solid content of the heat-resistant decorative coloring composition is not particularly limited, but is preferably 0.001 to 10% by mass, and preferably 0.01 to 1 The content is more preferably in the range of 0.05% to 0.2% by mass.

-solvent-
In addition, as the solvent for producing the coloring composition for heat-resistant decoration of the present invention, the solvents described in paragraphs 0043 to 0044 of JP-A-2011-95716 can be used.

-catalyst-
The heat-resistant and decorative coloring composition of the present invention contains a catalyst from the viewpoint of improving the brittleness of the decorative layer obtained by curing the heat-resistant and decorative coloring composition containing the silicone resin. preferable. In particular, when two or more silicone resins are used, they are preferably used to accelerate crosslinking by causing dehydration / dealcoholization condensation reaction.
A well-known thing can be used as said catalyst.
Preferred examples of the catalyst include tin (Sn), zinc (Zn), iron (Fe), titanium (Ti), zirconium (Zr), bismuth (Bi), hafnium (Hf), yttrium (Y) and aluminum (metal components). And organometallic compound catalysts such as organic complexes or organic acid salts of at least one metal selected from the group consisting of Al), boron (B) and gallium (Ga).
Among these, Sn, Ti, Zn, Zr, Hf, and Ga are preferable in that they have high reaction activity, Zn or Ti is more preferable from the viewpoint of preventing cracking at the time of baking, and Zn is particularly preferable from the viewpoint of pot life improvement.
Examples of the organic metal compound catalyst containing zinc (Zn) include zinc triacetylacetonate, zinc stearate, bis (acetylacetonato) zinc (II) (monohydrate) and the like.
As an example of the organometallic compound catalyst containing tin (Sn), titanium (Ti), zirconium (Zr), hafnium (Hf) and gallium (Ga), for example, the catalyst described in JP 2012-238636 A can be used. It can be used preferably.
A commercially available catalyst can also be used as said catalyst. For example, a zinc-based condensation catalyst D-15 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned.
In the present invention, one type of the catalyst may be used alone, or two or more types may be used in any combination and ratio. Moreover, you may use together with a reaction promoter or reaction inhibitor.
The content of the catalyst is preferably 0.01 to 10% by mass based on the silicone resin from the viewpoint of preventing cracking at the time of baking and improving the pot life, and more preferably 0.03 to 5.0. It is mass%.

-Additive-
Furthermore, other additives may be used in the heat-resistant decorative coloring composition. Examples of the additive include surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP2009-237362A, and thermal polymerization prevention described in paragraph 0018 of Japanese Patent No. 4502784. And further, other additives described in paragraphs [0058] to [0071] of JP-A-2000-310706.

As described above, the heat resistant decorative coloring composition in the present invention is mainly described as a non-photosensitive material, but the heat resistant decorative coloring composition may be a negative-working material or a positive-working material as needed. It may be

(Thickness)
When the heat resistant decorative coloring composition of the present invention is used as a decorative layer of a capacitive input device, the thickness when the heat resistant decorative coloring composition is applied is 1 to 40 μm It is preferable from the viewpoint of increasing the hiding power of the decorative layer.
The thickness of the decorative layer is more preferably 1.5 to 38 μm, particularly preferably 1.8 to 36 μm.

[Method of Manufacturing Capacitance Type Input Device]
The method for manufacturing a capacitance-type input device according to the present invention (hereinafter also referred to as the manufacturing method according to the present invention) comprises a front plate and at least one of the following (1) and (3) to (5) A method of manufacturing a capacitance-type input device having an element according to claim 1, wherein the heat-resistant and decorative coloring composition of the present invention is applied to one side of the front plate to form at least the (1) decorative layer. And the step of forming
(1) Decorative layer (3) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction through connection portions (4) The first transparent electrode pattern A plurality of second electrode patterns (5) comprising a plurality of pad portions which are electrically insulated and extend in a direction crossing the first direction (5) the first transparent electrode pattern and the second An insulating layer which electrically insulates from the electrode pattern of the electrode pattern according to the present invention may further have the following (6).
(6) A conductive element which is electrically connected to at least one of the first transparent electrode pattern and the second electrode pattern, and is different from the first transparent electrode pattern and the second electrode pattern. In the capacitance type input device of the present invention, the second electrode pattern may be a transparent electrode pattern. Although the second transparent electrode pattern may be described instead of the second electrode pattern in the present specification, the preferred embodiment of the second electrode pattern is the same as the preferred embodiment of the second transparent electrode pattern. is there.
Further, in the method of manufacturing a capacitance-type input device according to the present invention, on the surface opposite to the surface facing the front plate of the (1) decorative layer disposed on one side of the front plate, Furthermore, it is preferable to form (2) a mask layer.

<Configuration of Capacitance Type Input Device>
First, the configuration of a capacitive input device formed by the manufacturing method of the present invention will be described. FIG. 1 is a cross-sectional view showing a preferable configuration among the capacitance type input device of the present invention. In FIG. 1, the capacitive input device 10 includes a front plate 1, a decoration layer 2 a, a mask layer 2 b, a first transparent electrode pattern 3, a second transparent electrode pattern 4, and an insulating layer 5. , The conductive element 6 and the transparent protective layer 7.

The front plate 1 is made of a translucent substrate such as a glass substrate, and for example, tempered glass represented by Gorilla glass of Corning Co., Ltd. can be used. In the present specification, of the surfaces of the front plate 1 constituting the capacitance-type input device 10 of the present invention, the surface on which an input is performed by bringing a finger or the like into contact is referred to as a contact surface. The surface on the opposite side is called non-contact surface 1a. Hereinafter, the front plate may be referred to as a "substrate".

Further, a mask layer 2 b is provided on one surface of the front plate 1 via the decorative layer 2 a. The mask layer 2 b is a frame-like pattern around the display area formed on one surface side of the touch panel front plate, and is formed so as not to be visible in the routing wiring and the like.
The decorative layer 2a is formed on the mask layer 2b, that is, between the one surface side of the touch panel front plate and the mask layer 2b for the purpose of decoration.
In the capacitance-type input device 10 of the present invention, as shown in FIG. 2, a decorative layer 2a and a mask layer are provided to cover a partial region (a region other than the input surface in FIG. 2) of the front plate 1. Preferably 2b is provided. Furthermore, as shown in FIG. 2, the front plate 1 can be provided with an opening 8 in a part of the front plate. In the opening 8, a push-type mechanical switch can be installed. Since the tempered glass used as a base material is high in strength and difficult to process, in order to form the opening 8, it is general to form the opening 8 before the strengthening treatment and then to perform the strengthening treatment . However, if it is attempted to form the decorative layer 2a at one time using a liquid resist for forming a decorative layer or screen printing ink on the substrate after the strengthening treatment having the opening 8, leakage of the resist component from the opening may occur. Also, in the decorative layer provided between the mask layer and the front plate, which needs to form a light shielding pattern just above the boundary of the front plate, a resist component may be exfoliated (glare) from the glass edge to contaminate the back side of the front plate. Problems can occur. When forming the decorative layer 2a by dividing the coloring composition for heat resistant decoration into several times on the base material which has the opening part 8, such a problem can also be solved.

A plurality of first transparent electrode patterns 3 formed by extending a plurality of pad portions in a first direction through connection portions on one surface of the front plate 1, and a first transparent electrode pattern 3 And a plurality of second transparent electrode patterns 4 formed of a plurality of pad portions formed to extend in a direction intersecting the first direction, a first transparent electrode pattern 3 and a second And an insulating layer 5 that electrically insulates the transparent electrode pattern 4. 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). Metal oxide film. Examples of such a metal film include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, Mo and the like; metal oxide films such as SiO _{2 and the} like. At this time, the film thickness of each element can be 10 to 200 nm. In addition, since the amorphous ITO film is converted to a polycrystalline ITO film by firing, the electrical resistance can also be reduced. Moreover, the said 1st transparent electrode pattern 3, the 2nd transparent electrode pattern 4, and the electroconductive element 6 mentioned later are manufactured using the electroconductive curable resin composition using the below-mentioned electroconductive fiber. It can also be done. In addition, when forming the first transparent electrode pattern etc. by ITO etc., paragraphs 0014 to 0016 etc. of Japanese Patent No. 4506785 can be referred to.

Further, at least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4 is both on one side of the front plate 1 and on the opposite side of the surface of the mask layer 2 opposite to the front plate 1. It can be installed across the area. In FIG. 1, the second transparent electrode pattern is disposed across the two regions of one surface of the front plate 1 and the surface of the mask layer 2 opposite to the surface facing the front plate 1. It is shown. As described above, even in the case of covering the mask layer requiring a certain thickness and the back surface of the front plate, the coloring composition for heat-resistant decoration of the present invention is divided into several times and printed or applied. The process enables continuous film formation on the mask partial boundaries.

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 view showing an example of a first transparent electrode pattern and a second transparent electrode pattern in the present invention. As shown in FIG. 3, in the first transparent electrode pattern 3, the pad portion 3a is formed to extend 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 (second direction in FIG. 3) intersecting the first direction. It is comprised by the some pad part formed by existence. Here, when the first transparent electrode pattern 3 is formed, the pad portion 3a and the connection portion 3b may be manufactured integrally, or only the connection portion 3b is manufactured to form the pad portion 3a and the second portion. The transparent electrode pattern 4 may be integrally manufactured (patterned). When the pad portion 3a and the second transparent electrode pattern 4 are integrally manufactured (patterned), as shown in FIG. 3, a portion of the connection portion 3b and a portion of the pad portion 3a are connected, and an insulating layer Each layer is formed such that the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are electrically insulated by the reference numeral 5.

In FIG. 1, a conductive element 6 is provided on the surface of the mask layer 2 opposite to the surface facing the front plate 1. 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 the first transparent electrode pattern 3 and the second transparent electrode pattern 4 Another conductive element. In FIG. 1, a view is shown in which another conductive element 6 is connected to the second transparent electrode pattern 4.

Moreover, in FIG. 1, the transparent protective layer 7 is provided so that all of each component 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 the same material or different materials. As a material which comprises the insulating layer 5 and the transparent protective layer 7, a thing with high surface hardness and heat resistance is preferable, and a well-known photosensitive siloxane resin material, an acrylic resin material, etc. are used.

The details of each layer will be described below for the production method of the present invention.
Examples of embodiments formed in the process of the production method of the present invention include the embodiments of FIGS. FIG. 4 is a top view showing an example of the tempered glass 11 in which the opening 8 is formed. FIG. 5 is a top view showing an example of a front plate on which the decorative layer 2a and the mask layer 2b are formed. FIG. 6 is a top view showing an example of a 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 a conductive element 6 different from the first and second transparent electrode patterns is formed. These show examples that embody the above description, and the scope of the present invention is not limitedly interpreted by these drawings.

<(1) Decorative layer>
The manufacturing method of the present invention is characterized in that at least the (1) decorative layer (hereinafter also referred to as "colored layer") is formed using the heat resistant decorative coloring composition of the present invention.

In the capacitance type input device having the opening 8 of the configuration of FIG. 2, the decorative layer 2a described in FIG. 1, the mask layer described later, etc. When the transfer film having the photocurable resin composition or the photocurable resin layer of the present invention is used, there is no leakage of the resist component from the opening even in the substrate having the opening (front plate). In the decorative layer and mask layer where it is necessary to form a light shielding pattern, there is no protrusion of coloring components from the glass edge (moisture), so there is no contamination on the back of the front plate, and thinning and weight reduction in a simple process. It is possible to manufacture an integrated touch panel.

The method to form the said decoration layer using the coloring composition for heat resistant decoration of this invention is demonstrated. In general, when a heat-resistant decorative coloring composition is used, it can be formed by a conventional photolithography method as long as it contains a photocurable resin. Here, the coloring composition for heat-resistant decoration of the present invention may or may not contain a photocurable resin, and in any case, it is applied (for example, printed or coated) on a substrate. A decorative layer can be formed using the heat-resistant and decorative coloring composition of the present invention. It is preferable that printing of the coloring composition for heat-resistant decoration is performed by applying the coloring composition for heat-resistant decoration to one surface side of the front plate, and it is more preferable that it is screen printing.
If necessary, known developing equipment such as a brush and a high pressure jet may be combined. After development, post-exposure and post-baking may be carried out if necessary, and post-baking is preferred.

Moreover, after applying (for example, printing or application) the coloring composition for heat resistance decoration of this invention, in order to improve the adhesiveness of the decoration layer in a drying process, one side of a base material (front plate) beforehand Surface treatment. As the surface treatment, it is preferable to carry out surface treatment (silane coupling treatment) using a silane compound (silane coupling agent). As a silane coupling agent, what has a functional group which interacts with photosensitive resin is preferable. For example, a silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3 wt% aqueous solution, trade name: KBM 603, Shin-Etsu Chemical Co., Ltd.) is sprayed for 20 seconds with a shower to wash the pure water shower Do. After this, the reaction is carried out by heating. A heating tank may be used, and the reaction can be promoted by preheating the substrate of the laminator.

(Post-bake process)
It is preferable to include a post-baking step after the drying step after applying (for example, printing or coating) the heat-resistant decorative coloring composition to one surface side of the front plate.
The manufacturing method of the present invention is the environment of 0.08 to 1.2 atm after applying the coloring composition for heat-resistant decoration of the present invention to one side of the front plate of the (1) decorative layer. It is preferable to form by heating to 180 to 300 ° C. below from the viewpoint of achieving both whiteness and productivity.
The post-baking heating is more preferably performed under an environment of 0.5 atm or more. On the other hand, it is more preferable to carry out under an environment of 1.1 atm or less, and it is particularly preferable to carry out under an environment of 1.0 atm or less. Furthermore, it is particularly preferable to carry out under about 1 atm (atmospheric pressure) environment from the viewpoint of reducing the manufacturing cost without using a special pressure reducing device. Here, conventionally, when the above-mentioned (1) decorative layer is cured by heating and formed, it is performed under a reduced pressure environment with very low pressure, and the whiteness after baking is maintained by lowering the oxygen concentration. However, by using the heat-resistant and decorative coloring composition of the present invention, the whiteness of the decorative layer can be enhanced even after baking in the above pressure range.
The temperature of the post-baking is more preferably 200 to 280 ° C., and particularly preferably 220 to 260 ° C.
The post-baking time is more preferably 20 to 150 minutes, and particularly preferably 30 to 100 minutes.
The post-baking may be performed in an air environment or in a nitrogen-substituted environment, but it is particularly preferable to perform in an air environment from the viewpoint of reducing the manufacturing cost without using a special pressure reducing device.

(Other process)
The manufacturing method of the present invention may have other steps such as a post-exposure step.
When the heat-resistant decorative coloring composition has a photocurable resin layer, it is preferable to include a post-exposure step when forming the decorative layer. In the post-exposure step, the surface of the decorative layer may be exposed from the side facing the front plate, or the side opposite to the side facing the front plate may be exposed. Alternatively, the exposure may be performed from both sides of the decorative layer.

<(2) Mask layer>
In the manufacturing method of the present invention, the mask layer 2b, the first transparent electrode pattern 3, the second transparent electrode pattern 4, the insulating layer 5, the conductive element 6, and the transparent protective layer 7 as needed. It is preferable to form at least one of the components by using a curable resin composition. Further, by transferring a transfer film having a curable resin layer formed using a curable resin composition, the mask layer 2b, the first transparent electrode pattern 3, the second transparent electrode pattern 4, and the insulation It is also preferable to include the step of forming at least one element of the layer 5, the conductive element 6, and, if necessary, the transparent protective layer 7. In addition, with "curable resin layer", the "photocurable resin which consists of a layer (decorative layer) obtained by forming into a film the coloring composition for heat resistance decoration of this invention, and a photocurable resin composition. "Layer" is included.
At least one of the mask layer 2b, the first transparent electrode pattern 3, the second transparent electrode pattern 4, the insulating layer 5, the conductive element 6, and, if necessary, the transparent protective layer 7 is light. It is more preferable to form by forming a curable resin layer, and it is particularly preferable to form using a photocurable resin composition.
For example, in the case of forming a black mask layer 2, the surface of the front plate 1 may be formed using a black coloring composition as the decorative layer or a photocurable resin composition having a black photocurable resin layer. The black decorative layer can be formed on

Further, by using the photocurable resin composition for forming the mask layer 2b which needs light shielding property, it is possible to form a high quality mask layer 2b and the like without light leakage due to unevenness, repelling, air bubbles and the like.

A coloring agent can be used when using the coloring layer which consists of a coloring composition, and the photocurable resin layer which consists of said photocurable resin composition as a mask layer. As a coloring agent used for this invention, a well-known coloring agent (an organic pigment, an inorganic pigment, dye etc.) can be used suitably. In the present invention, a mixture of pigments such as white, black, red, blue and green can be used.
In particular, when the mask layer is used as a black mask layer, it is preferable to use a black colorant from the viewpoint of optical density. Examples of black colorants include carbon black, titanium carbon, iron oxide, titanium oxide, graphite and the like, among which carbon black is preferred.
In order to use as a mask layer of other colors, the pigment described in paragraphs 0183 to 0185 of Japanese Patent No. 4546276, or a dye may be mixed and used. Specifically, pigments and dyes described in paragraphs 0038 to 0054 of JP 2005-17716 A, pigments described in paragraphs 0068 to 0072 of JP 2004-361447 A, paragraphs of JP 2005-17521 A. The colorants described in 0080 to 0088 can be suitably used.
From the viewpoint of dispersion stability, the colorant used in the present invention other than the decorative layer 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 term "particle size" as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and "number average particle size" refers to the above-described particle size of a large number of particles, This 100-piece average value is said.

It is preferable that a photocurable resin layer is the following structures.

The monomer used for the photocurable resin layer is not particularly limited as long as it does not depart from the spirit of the present invention, and a known polymerizable compound can be used.
As the polymerizable compound, those described in paragraphs 0023 to 0024 of Patent No. 4098550 can be used.

The binder used in the photocurable resin layer is not particularly limited as long as it does not depart from the spirit of the present invention, and a known polymerizable compound can be used.
When the photocurable resin composition is a negative-working material, the photocurable resin composition preferably contains an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. Further, colorants, additives, etc. may be used, but not limited thereto.
As the alkali-soluble resin, the polymers described in paragraph 0025 of JP-A-2011-95716 and paragraphs 0033 to 0052 of JP-A-2010-237589 can be used.
When the photocurable resin composition is a positive type material, for example, a material described in JP-A-2005-221726 or the like is used for the photocurable resin layer, but it is not limited thereto.

As the photopolymerization initiator used in the photocurable resin layer, the polymerizable compounds described in paragraphs 0031 to 0042 of JP-A-2011-95716 can be used.

-Additive-
Furthermore, the photocurable resin layer may use an additive. Examples of the additive include surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP2009-237362A, and thermal polymerization prevention described in paragraph 0018 of Japanese Patent No. 4502784. And further, other additives described in paragraphs [0058] to [0071] of JP-A-2000-310706.

-solvent-
Further, as the solvent of the photocurable resin composition, the solvents described in paragraphs 0043 to 0044 of JP-A-2011-95716 can be used.

As mentioned above, although the case where the photocurable resin composition was a negative type material was mainly demonstrated, the said photocurable resin composition may be a positive type material.

<(3) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction through a connection portion>

In the method of manufacturing a capacitive input device according to the present invention, at least one of the first transparent electrode pattern, the second transparent electrode pattern, and the conductive element is formed of a photocurable resin composition. It is preferable to form by etching-processing a transparent conductive material using an etching pattern.
On the other hand, in the method of manufacturing a capacitive input device according to the present invention, a conductive curable resin layer is formed on at least one of the first transparent electrode pattern, the second electrode pattern, and the conductive element. It is preferable that it is made, and it is more preferable to form using electroconductive curable resin composition.
That is, it is preferable to form the said 1st transparent electrode pattern 3 using an etching process or electroconductive curable resin composition.

(Etching process)
When forming the said 1st transparent electrode pattern 3 by an etching process, there is no restriction | limiting in particular in the method of an etching process, For example, on one side of the front plate 1 in which the mask layer 2b etc. were formed first A transparent electrode layer is formed by sputtering, and then a film is formed using the composition having a photocurable resin for etching on the transparent electrode layer, and then an etching pattern is formed by mask exposure and development, and then the transparent electrode is formed. A method of forming the first transparent electrode pattern 3 or the like can be mentioned by etching the layer to pattern the transparent electrode and removing the etching pattern.
Before forming a film of a composition having a photocurable resin for etching on the transparent electrode layer, the front plate is inserted into the antifouling plate 13 shown in FIG. 10, and the substrate is opened as shown in FIG. If it has, it is preferable to insert the antifouling plug 14 shown in FIG. 11 into the opening. The stain preventing plate and the stain preventing plug are preferably made of silicone.
Also when using the transfer film which has the said photocurable resin layer as an etching resist (etching pattern), it can carry out similarly to the said method, and can obtain a resist pattern. As the etching, etching and resist peeling can be applied by a known method described in, for example, paragraphs 0048 to 0054 of JP-A-2010-152155.

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

The temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or less. The resin pattern used as an etching mask (etching pattern) in the present invention is formed using the above-mentioned coating liquid for photo-curable resin layer for etching, whereby acidic and alkaline etching in such a temperature range is carried out. Exhibits particularly good resistance to fluids. Therefore, peeling of the resin pattern during the etching process is prevented, and the portion where the resin pattern does not exist is selectively etched.
After the etching, a washing step and a drying step may be performed as necessary to prevent line contamination. For the cleaning process, for example, the substrate is washed with pure water at normal temperature for 10 to 300 seconds, and for the drying process, the air blow pressure (about 0.1 to 5 kg / cm ² ) is appropriately adjusted using an air blow. You should do it.

Next, the method of peeling the resin pattern is not particularly limited, and for example, a method of immersing the base material in the peeling solution being stirred at 30 to 80 ° C., preferably 50 to 80 ° C. for 5 to 30 minutes may be mentioned. The resin pattern used as an etching mask in the present invention exhibits excellent chemical solution resistance at 45 ° C. or lower as described above, but exhibits a property of being swelled by an alkaline peeling solution at a chemical solution temperature of 50 ° C. or higher. . Due to such properties, when the peeling process is performed using a peeling solution at 50 to 80 ° C., the process time is shortened and there is an advantage that the peeling residue of the resin pattern is reduced. That is, by providing a difference in chemical solution temperature between the etching process and the peeling process, the resin pattern used as an etching mask in the present invention exhibits good chemical liquid resistance in the etching process, while the resin pattern in the peeling process It will exhibit good releasability, and both conflicting properties of chemical resistance and releasability can be satisfied.

As the peeling solution, for example, inorganic alkali components such as sodium hydroxide and potassium hydroxide, organic alkali components such as tertiary amine and quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or these And a stripping solution dissolved in a mixed solution of It may be peeled off by a spray method, a shower method, a paddle method or the like using the above-mentioned stripping solution.

(Method using conductive curable resin layer)
Moreover, a 1st transparent electrode layer, a 2nd transparent electrode layer, and another electroconductive member can also be formed, using a curable resin layer as a lift-off material. In this case, after a curable resin layer is formed using application of a photocurable resin composition or transfer of a photocurable resin on a temporary support, and after patterning, a transparent conductive layer is formed on the entire surface of the substrate, A desired transparent conductive layer pattern can be obtained by dissolving and removing the deposited transparent conductive layer and the photocurable resin layer (lift-off method).

The conductive curable resin layer contains conductive fibers and the like.

-Conductive curable resin layer (conductive fiber)-
When the transfer film in which the conductive curable resin layer is laminated is used for forming a transparent electrode pattern or another conductive element, the following conductive fibers can be used for the conductive curable resin layer.

There is no restriction | limiting in particular as a structure of a conductive fiber, Although it can select suitably according to the objective, Either a solid structure and a hollow structure are preferable.
Here, fibers of solid structure may be referred to as "wires" and fibers of hollow structures may be referred to as "tubes". In addition, conductive fibers having an average minor axis length of 1 nm to 1,000 nm and an average major axis length of 1 μm to 100 μm may be referred to as “nanowires”.
In addition, conductive fibers having a hollow structure and having an average minor axis length of 1 nm to 1,000 nm and an average major axis length of 0.1 μm to 1,000 μm 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, but at least one of metal and carbon is preferable, and among them, the above 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, and is preferably, 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 period table (IUPAC 1991), At least one metal selected from Groups 2 to 14 is more preferable, and

Groups

2, 8, 9, 9, 10, 11, 12, 12, 13, and 14 are preferable. Further preferred is at least one metal selected from the group consisting of at least one metal, particularly preferably 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, tantalum, titanium, bismuth, antimony, lead , These alloys and the like. Among these, from the point of being excellent in conductivity, one containing silver mainly or one containing an alloy of silver and a metal other than silver is preferable.
Mainly containing silver means that the metal nanowires contain 50% by mass or more, preferably 90% by mass or more of silver.
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--
The shape of the metal nanowire is not particularly limited and may be appropriately selected according to the purpose. For example, it may have an arbitrary shape such as a cylindrical shape, a rectangular solid shape, or a columnar shape whose cross section is a polygon. In applications where high transparency is required, a cylindrical shape, and a cross-sectional shape in which the corners of the cross-sectional polygon are rounded are preferable.
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 refers to the periphery 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 the adjacent corners and the corners. In this case, the ratio of the “peripheral length of the cross section” to the total length of the “sides of the cross section” is 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 shown by the solid line and the outer peripheral length of the pentagon shown by the dotted line. A cross-sectional shape having a sharpness of 75% or less is defined as a cross-sectional shape with rounded corners. The degree of sharpness is preferably 60% or less, more preferably 50% or less. If the degree of sharpness exceeds 75%, electrons may be localized at the corners, and plasmon absorption may increase, or yellowness may remain, resulting in deterioration of transparency. In addition, the linearity of the edge portion of the pattern may be reduced to cause rattling. The lower limit of the sharpness is preferably 30%, and more preferably 40%.

-Average minor axis length and average major axis length-
The average minor axis length (sometimes referred to as “average minor axis diameter” or “average diameter”) of the metal nanowires is preferably 150 nm or less, more preferably 1 nm to 40 nm, and still more preferably 10 nm to 40 nm. 15 nm to 35 nm is particularly preferred.
If the average minor axis length is less than 1 nm, oxidation resistance may deteriorate and durability may deteriorate. If it exceeds 150 nm, scattering due to metal nanowires may occur to obtain sufficient transparency. There are things I can not do.
The average minor axis length of the metal nanowires was determined by observing 300 metal nanowires using a transmission electron microscope (TEM; JEM-2000FX, manufactured by Nippon Denshi Co., Ltd.), and based on the average value, the metal nanowires The average minor axis length of was determined. In the case where the minor axis of the metal nanowire is not circular, the longest minor axis is defined as the minor axis length.

The average major axis length (sometimes referred to as “average length”) of the metal nanowires is preferably 1 μm to 40 μm, more preferably 3 μm to 35 μm, and still 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, and if it exceeds 40 μm, the metal nanowire is too long to be produced. Occasionally, entanglement may occur during the manufacturing process.
The average major axis length of the metal nanowires can be determined, for example, by observing 300 metal nanowires using a transmission electron microscope (TEM; JEM-2000FX, manufactured by Nippon Denshi Co., Ltd.), and based on the average value, metal nano The average major axis length of the wire was determined. In addition, when the said metal nanowire is bent, the circle | round | yen which makes it an arc is considered and the value calculated from the radius and curvature was made into long-axis length.

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

<(4) A plurality of second electrode patterns comprising a plurality of pad portions electrically insulated from the first transparent electrode pattern and extending in a direction intersecting the first direction>

The second electrode pattern is preferably a transparent electrode pattern. The second transparent electrode pattern 4 can be formed using the etching process or a transfer film having the conductive curable resin layer. A preferable mode at that time is the same as the method of forming the first transparent electrode pattern 3.

<(5) Insulating Layer for Electrically Insulating the First Transparent Electrode Pattern and the Second Transparent Electrode Pattern>
When forming the insulating layer 5, it has a transfer film having an insulating colored layer as the colored layer, an insulating colored composition, and an insulating photocurable resin layer as the photocurable resin layer. The insulating colored layer or the photocurable resin layer on the surface of the front plate 1 on which the first transparent electrode pattern is formed by using the transfer film or the photocurable resin composition having the photocurable resin layer Can be formed.
When the insulating layer is formed, the thickness of the insulating layer is preferably 0.1 to 5 μm, more preferably 0.3 to 3 μm, and particularly preferably 0.5 to 2 μm, from the viewpoint of maintaining insulation.

<(6) electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern, and a conductivity different from the first transparent electrode pattern and the second transparent electrode pattern Element>
The said another conductive element 6 can be formed using the transfer film or the conductive curable resin composition which has the said etching process or the said conductive curable resin layer.

<(7) Transparent Protective Layer>
When forming the transparent protective layer 7, each element is formed using a transfer film or a photocurable resin composition having the photocurable resin layer having a transparent photocurable resin layer as the photocurable resin layer. It forms by transferring the said transparent colored layer or a transparent photocurable resin layer on the surface of the said front plate 1 in which this was formed.
When forming a transparent protective layer using a transfer film, the layer thickness of the transparent protective layer is preferably 0.5 to 10 μm, more preferably 0.8 to 5 μm, from the viewpoint of exhibiting sufficient surface protective ability. ~ 3 μm is particularly preferred.

<< Capacitance-type input device and image display device provided with capacitance-type input device as components >>
An electrostatic capacitance type input device obtained by the manufacturing method of the present invention and an image display device provided with the electrostatic capacitance type input device as a component are the "latest touch panel technology" (July 6, 2009 issue) Techno Times), supervised by Yuji Mitani, “Touch panel technology and development”, CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292 etc. It can apply.

Hereinafter, the present invention will be more specifically described by way of examples.
The materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as limited by the specific examples shown below. In addition, unless there is particular notice, "%" and "part" are mass references.

Synthesis Example 1
<Synthesis of Tolyltrimethoxysilane ((4-methylphenyl) trimethoxysilane)>
In a 500 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 19.0 g (0.784 mol) of magnesium and 300 mL of tetrahydrofuran were added, and then an iodine piece was added thereto. After a small amount of tolyl chloride was added dropwise to initiate the reaction, a total of 94.4 g (0.746 mol) of tolyl chloride was added dropwise at 5-10 ° C. to prepare a Grignard reagent.

Next, to a 1000 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 568 g (3.73 mol) of methyl orthosilicate was added and prepared at a temperature of 60 to 70 ° C. The Grignard reagent was added dropwise over 2 hours. After cooling, the precipitated magnesium salt was filtered. Then, the solvent was distilled off and further rectified and recovered. As a result of GC analysis of the obtained fraction, GC purity was 98.8%, and as a result of NMR analysis and IR analysis, it was confirmed that tolyltrimethoxysilane (bp 74 to 75 ° C.) was obtained. .

(Synthesis of tolyltrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% condensate)
To a 500 mL four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, add 2.1 g of 25% aqueous tetramethylammonium hydroxide solution and 7.5 g of water, and then 60 mL of 2-propanol and toluene Added 30 mL. Thereto, 30 mL of a toluene solution of 26.6 g (0.195 mol) of methyltrimethoxysilane and 17.8 g (0.084 mol) of tolyltrimethoxysilane is placed in a dropping funnel and added dropwise at a temperature of 35 to 45 ° C. while stirring. did. After completion of the dropwise addition, aging was performed for 2 hours, and after cooling to room temperature, 90 mL of toluene and 90 mL of water were added to the solution after cooling to extract a product. After pouring into a separatory funnel and draining the aqueous phase, the organic phase was washed with dilute aqueous acetic acid solution, and after draining the aqueous phase, the organic phase was washed four times with water. Thereafter, the organic phase was filtered with a 0.5 μm PTFE filter and concentrated to prepare a 50 mass% toluene solution to obtain a toluene solution of tolyltrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% condensate.

Synthesis Example 2
<Synthesis of benzyltrimethoxysilane>
Benzyltrimethoxysilane was prepared in the same manner as in Synthesis Example 1 except that, in Synthesis Example 1, equimolar amounts of benzyl chloride were used instead of tolyl chloride.

(Synthesis of benzyltrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% condensate)
Tolyltrimethoxysilane / methyl except for using equimolar amounts of benzyltrimethoxysilane instead of tolyltrimethoxysilane in the synthesis of the 30 mol% / 70 mol% condensate of the aforementioned tolyltrimethoxysilane / methyltrimethoxysilane of Synthesis Example 1 In the same manner as in the synthesis of trimethoxysilane 30 mol% / 70 mol% condensate, a toluene solution of benzyltrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% condensate was obtained.

Synthesis Example 3
<Synthesis of cumyltrimethoxysilane>
Cumyltrimethoxysilane was prepared in the same manner as in Synthesis Example 1 except that, in Synthesis Example 1, equimolar amounts of cumyl chloride were used instead of tolyl chloride.

(Synthesis of cumyltrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% condensate)
In the synthesis of the 30 mol% / 70 mol% condensate of the above-mentioned tolyltrimethoxysilane / methyltrimethoxysilane of Synthesis Example 1, tolyltrimethoxysilane / methyl except for using equimolar amount of cumyltrimethoxysilane instead of tolyltrimethoxysilane In the same manner as in the synthesis of the trimethoxysilane 30 mol% / 70 mol% condensate, a toluene solution of cumyltrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% condensate was obtained.

Synthesis Example 4
(Synthesis of tolyltrimethoxysilane / ethyltrimethoxysilane 30 mol% / 70 mol% condensate)
In the same manner as in Synthesis Example 1 except that ethyltrimethoxysilane was used in place of methyltrimethoxysilane in Synthesis Example 1 in the same manner as in Synthesis Example 1, a toluene solution of tolyltrimethoxysilane / ethyltrimethoxysilane 30 mol% / 70 mol% condensate I got

Synthesis Example 5
(Synthesis of tolyltrimethoxysilane / propyltrimethoxysilane 30 mol% / 70 mol% condensate)
Tolyltrimethoxysilane / propyltrimethoxysilane 30 mol% / 70 mol% in the same manner as in Synthesis Example 1 except that instead of methyltrimethoxysilane in Synthesis Example 1 an equimolar amount of propyltrimethoxysilane (Synthesis example 5) was used. A toluene solution of the condensate was obtained.

Synthesis Example 6
(Synthesis of methyltrimethoxysilane / methyldimethoxysilane 90 mol% / 10 mol% condensate)
In the synthesis of the tolyltrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% condensate of the synthesis example 1, the total number of moles of tolyltrimethoxysilane / methyltrimethoxysilane added is kept constant while maintaining the total number of moles of tolyltrimethoxysilane / methyltrimethoxysilane constant. The same as in the synthesis of the tolyltrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% condensate except that the molar ratio of the acid to the methyldimethoxysilane is 90 mol% / 10 mol% is the same as the synthesis of the tomethyltrimethoxysilane / A toluene solution of methyldimethoxysilane 90 mol% / 10 mol% condensation product (methyl hadorogen type silicone resin) was obtained.

Example 1
Preparation of the heat resistant decorative coloring composition of the present invention
The heat resistant decorative coloring composition of the following formulation L1 was prepared and used as the heat resistant decorative coloring composition of Example 1.
(Colorable composition for heat resistant decoration: prescription L1)
Silicone resin KR-311 (Shin-Etsu Chemical Co., Ltd. product; straight silicone in xylene solution (solid content: 50% by mass): 209 parts by mass White pigment dispersion 1 (the following composition): 123 parts by mass Agent (Phosphoric acid / Hindered phenolic antioxidant, Sumilizer GP, Sumitomo Chemical Co., Ltd.)
: 0.195 parts by mass, surfactant (trade name: Megafac F-780F, manufactured by DIC Corporation)
: 0.78 parts by mass

-Composition of White Pigment Dispersion 1-
· Titanium oxide (CR-97 manufactured by Ishihara Sangyo; alumina / zirconia-treated rutile type,
Primary particle size 0.25 μm): 70.0 mass%
-Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, weight average molecular weight 37,000): 3.5 mass%
-Methyl ethyl ketone (manufactured by Tonen Chemical Co., Ltd.): 26.5 mass%

<< Formation of Decorative Layers >>
With a rotating brush with nylon hair while spraying a glass detergent solution adjusted to 25 ° C with a shower for 20 seconds on a tempered glass (glass substrate: 300 mm x 400 mm x 0.7 mm) in which an opening (15 mm 形成) was formed After washing and showering with pure water, a shower of silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% by weight aqueous solution, trade name: KBM 603, Shin-Etsu Chemical Co., Ltd.) is performed. The spray was performed for 20 seconds, and the pure water shower was washed. The glass substrate was heated at 110 ° C. for 10 minutes with a substrate preheating device and then allowed to cool to room temperature. Using the color composition for heat resistance decoration (formulation L1) on the obtained silane coupling treated glass substrate, a printing ink is printed using a screen printing machine (made by Mishima Co., Ltd .; UDF-5L, mesh size 250 μm) It screen-printed in the frame pattern shape, and obtained the tack-free white colored layer by drying at 100 degreeC for 10 minutes. The thickness of the white colored layer after ink drying was 6 μm. Furthermore, in the same manner as described above, printing ink was screen-printed in the form of a frame pattern on the white colored layer, and the steps of drying at 100 ° C. for 10 minutes were repeated, and printing and drying steps were performed six times in total. Furthermore, it dried at 150 degreeC for 30 minutes, and obtained the white colored layer L1.

Then, using an oven equipped with an exhaust system, post bake processing is performed at 240 ° C. for 60 minutes in air under atmospheric pressure (1 atm) to make the white colored layer L1 a decorative layer, and the decorative layer is formed by the following method When the film thickness was measured, the front plate in which the decoration layer with a film thickness of 36 micrometers was formed was obtained.
When the lightness was measured by the following method from the surface of the front plate on which the decorative layer was not formed, the L value was 84.6. Moreover, when the whiteness degree of the decoration layer of a front plate was judged visually with the following method, there was no problem. Furthermore, the benzene generation amount at the time of post-baking treatment by the following method was a practical level at 19.1 mg per 100 cm ² of the decorative layer.

(Film thickness measurement)
The film thickness of the decorative layer in the front plate having the decorative layer formed on the tempered glass was measured using a surface roughness measuring device P-10 (manufactured by TENCOR). The results are shown in Table 1 below. In Table 1 below, "μ" means "μm".

<< Evaluation of the front board which formed the decoration layer >>
(Evaluation of lightness)
In the front plate in which a decorative layer is formed on a tempered glass, the L value is measured using a 938 Spectrodensitometer manufactured by X-Rite with a black paper as a base from the surface opposite to the surface on which the decorative layer is formed. The lightness was evaluated according to the following evaluation criteria. The practical level is D or more, preferably C or more.
<Evaluation criteria>
AA: L value is 87 or more.
A: L value is 85 or more and less than 87.
B: L value is 83 or more and less than 85.
C: L value is 81 or more and less than 83.
D: L value is 77 or more and less than 81.
E: L value is less than 77.
The evaluated results are shown in Table 1 below.

(Evaluation of whiteness)
After forming the decorative layer on the tempered glass as described above, 60 persons observed the front plate formed by post-baking treatment at 240 ° C. for 60 minutes in air under atmospheric pressure (1 atm) from both sides The whiteness was evaluated according to the following evaluation criteria. The practical level is C or higher.
<Evaluation criteria>
A: Number of people who recognized yellowishness 0 to 1 B: Number of people who recognized yellowishness 2 to 3 C: Number of people who recognized yellowishness 4 to 5 D: Number of people who recognized yellowishness: 6 to 10 E: Number of people who recognized yellowishness: 11 or more The evaluation results of the white colored layer L1 are shown in Table 1 below.

(Reticulation evaluation)
After leaving the front plate having the decorative layer formed on the tempered glass to stand for 24 hours under an environment of 23 ° C. and a relative humidity of 50%, the surface of the decorative layer of the front plate and the opposite side of the surface having the decorative layer formed The surface was observed with a microscope using reflected light and transmitted light, and reticulation evaluation was performed according to the following criteria. C or more is a practical level.
<Evaluation criteria>
A: The occurrence of fine "wrinkles" and extremely weak "wrinkles" was not observed at all on the surface of the decorative layer pattern of the front plate, which is extremely good.
B: The occurrence of extremely weak "wrinkles" was observed only in a part of the central part (central part in the width direction) of the decorative layer pattern surface of the front panel, but from the opposite surface of the surface on which the decorative layer was formed Is unrecognizable and good.
C: Generation of fine "wrinkles" was slightly recognized on the surface of the decorative layer pattern surface of the front panel, but it can not be recognized from the opposite surface of the surface of the front panel on which the decorative layer was formed. Well, normal.
D: The occurrence of fine "wrinkles" was considerably observed on the surface of the decorative layer pattern of the front panel, and weak unevenness was also observed from the opposite surface of the surface of the front panel on which the decorative layer was formed.
E: The occurrence of fine “wrinkles” etc. is observed on the entire surface of the decorative layer pattern surface of the front panel, and unevenness is observed also from the opposite surface of the surface on which the decorative layer of the front panel is formed.
The evaluation results of the front plate are listed in Table 1 below.

(Evaluation of the rate of return)
Five hundred front plates having a decorative layer formed on a tempered glass were prepared, and the yield of usable ones was examined.
<Evaluation criteria>
A: The yield was over 94%, which was a very good level.
B: The yield was 91% or more and less than 94, which was a good level.
C: The yield was 88% or more and less than 91%, which was a normal level.
D: The yield was 83% or more and less than 88%, which was a bad level.
E: The yield was less than 83%, which was a very bad level.
The evaluation results of the front plate are listed in Table 1 below.

(Evaluation of decorative layer adhesion)
In a decorative layer of a front plate having a decorative layer formed on a tempered glass in accordance with JIS K 5600-5-6: ISO 2409 (cross-cut method), a cut was made with a width of 1 mm to form a grid. The peeling test of the decorative layer was performed using cellophane tape (Cellotape plant CT-18, manufactured by Nichiban Co., Ltd.) to observe whether the surface of the decorative layer had peeled off or pinholes were present. C or more is a practical level.
<Evaluation criteria>
A: The decorative layer component did not peel at all, and the adhesion was at a very good level.
B: There was slight peeling of the decorative layer component only at the edge portion of the incision, but there was no peeling of the decorative layer component at all at the mesh portion, and the adhesion was at a good level.
C: Peeling off of the decorative layer component was observed in the area of squares and 0% or more and less than 2%, and the adhesion was at a normal level.
D: Peeling off of the decorative layer component was observed in the area of 2 or more and less than 5%, and the adhesion was at a poor level.
E: Peeling off of the decorative layer component was observed at 5% or more at the portion of the grid, and the adhesion was at a very poor level.
The evaluation results of the front plate are listed in Table 1 below.

(Evaluation of opening dirt)
The periphery of the opening edge of the front plate in which the decorative layer was formed on the tempered glass was observed with a microscope, and it was observed whether or not the decorative layer component was present as dirt. C or more is a practical level.
<Evaluation criteria>
A: The edge of the opening is not stained at all by the component of the decorative layer and is extremely good.
B: A slight stain of the component of the decorative layer was observed only at the edge of the opening, but it was good at a usable level.
C: Staining of the component of the decorative layer was observed from the edge of the opening to several micrometers in the thickness direction of the glass, but it is practically usable and practical.
D: Staining of the component of the decorative layer is observed from the edge of the opening to the middle of the thickness of the glass, which is bad.
E: From the edge of the opening to the back side of the glass, contamination of the components of the decorative layer is observed, which is very bad.
The evaluation results of the front plate are listed in Table 1 below.

(Evaluation of missing opening)
The periphery of the opening edge of the front plate in which the decorative layer was formed on the tempered glass was observed with a microscope, and the peeling of the decorative layer component and the presence of pinholes were observed.
<Evaluation criteria>
A: There was no peeling of the decorative layer component of the substrate in the vicinity of the opening, which was a very good level.
B: There was slight peeling off of the decorative layer component only at the opening edge, but there was no other part at all, and it was at a good level.
C: Peeling of the decoration layer component was observed in the range of several μm width around the opening edge, but it can be practically used and is common.
D: Peeling of the decorative layer component is observed in the range of several mm width around the opening edge, which is bad.
E: Peeling of the decorative layer component is observed in the range of several cm width around the opening edge, which is very bad.
The evaluation results of the front plate are listed in Table 1 below.

(Benzene generation amount)
The heat resistant decorative coloring composition (formulation L1) was applied onto the tempered glass. Next, it was dried in an oven at 105 ° C. for 30 minutes to obtain a tempered layer-containing tempered glass. After a fixed area of the decorative layer is scraped from the tempered glass, placed in a sample tube, and heated directly under He gas at 280 ° C. for 15 minutes (including the temperature rising time from room temperature) using a heating / desorber, GC-MS measurements were performed.
For the calibration curve, commercially available benzene (reagent) was used, and after being collected in the TENAX adsorption tube by the existing method, the thermal desorption measurement similar to the sample was performed.
The GC column was maintained at 40 ° C. for 3 minutes using DB-5MS manufactured by Agilent, and then the temperature was measured. MS detection was performed by EI ionization, and for quantification, the chromatographic peak area of benzene was used.
・ Heat desorber Company name Japan analysis industrial equipment name Heat desorber Model JTD-505III
GC-MS
Company Name Shimadzu Equipment Name Gas Chromatograph Mass Spectrometer Model QP2010 Ultra
<Evaluation criteria>
AA: The generation of benzene was very good at less than 0.01 mg / 100 cm ² .
A: The benzene generation amount was as good as 0.01 mg / 100 cm ² or more and less than 9.2 mg / 100 cm ² .
B: The benzene generation amount was normal at 9.2 mg / 100 cm ² or more and less than 19 mg / 100 cm ² .
C: Benzene generation amount is 19 mg / 100 cm ² or more, less than 29 mg / 100 cm ² , practically usable and practical.
D: The benzene generation amount is not good at 29 mg / 100 cm ² or more.
The evaluation results of the front plate are listed in Table 1 below.

<< Formation of Mask Layer >>
Preparation of Coating Liquid for Forming Mask Layer
Coating solution for forming a mask layer shown below: Formulation K1 was prepared.

(Coating liquid for mask layer formation: prescription K1)
K pigment dispersion 1 (the following composition): 31.2 parts by mass R pigment dispersion 1 (the following composition): 3.3 parts by mass MMPGAc (propylene glycol monomethyl ether acetate, manufactured by Daicel Chemical Industries, Ltd.) 6.2 parts by mass Methyl ethyl ketone (manufactured by Tonen Chemical Co., Ltd.): 34.0 parts by mass Cyclohexanone (manufactured by Kanto Denka Kogyo Co., Ltd.): 8.5 parts by mass Binder 2 (benzyl methacrylate / methacrylic acid = 78 Random copolymer at a ratio of 22/22, weight average molecular weight 38,000: 10.8 parts by mass Phenothiazine (manufactured by Tokyo Kasei Kogyo Co., Ltd.): 0.01 parts by mass DPHA (dipentaerythritol hexaacrylate, Japan Propylene glycol monomethyl ether acetate solution (76 mass%) of Kayaku Co., Ltd. product
5.5 parts by mass 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bis (ethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine: 0.4 Mass part, surfactant (trade name: Megafac F-780F, manufactured by Dainippon Ink Co., Ltd.)
: 0.1 parts by mass

-Composition of pigment dispersion 1-K-
Carbon black (trade name: Nipex 35, manufactured by Degussa): 13.1% by mass
· The following dispersant 1: 0.65% by mass
Binder 1 (benzyl methacrylate / random copolymer of methacrylic acid = 72/28 molar ratio, weight average molecular weight 37,000): 6.72 mass%
Propylene glycol monomethyl ether acetate: 79.53% by mass

Composition of -R Pigment Dispersion 1-
-Pigment (CI pigment red 177): 18% by mass
· Binder 1 (benzyl methacrylate / random copolymer of methacrylic acid = 72/28 molar ratio, weight average molecular weight 37,000): 12% by mass
Propylene glycol monomethyl ether acetate: 70% by mass

<Formation of mask layer>
The front plate on which the decorative layer was formed was cleaned in the same manner as the cleaning of the tempered glass substrate in the formation of the decorative layer.
The above coating solution for forming a mask layer: The printing ink is screen-printed in a frame pattern with a screen printer (made by Mishima Co., Ltd .; UDF-5L, mesh size 250 μm) using a prescription K1, and dried at 100 ° C. for 10 minutes Thus, a tack-free mask layer was obtained. The thickness of the mask layer after ink drying was 2.2 μm. Then, it was exposed with an exposure dose of 1000 mJ / cm ² (i-line) without using an exposure mask with a proximity type exposure apparatus (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp.
Further, a post-baking treatment is performed at 240 ° C. for 80 minutes, and before a mask layer having an optical density of 4.0 and a film thickness of 2.0 μm and a decoration layer are formed in the order of the front plate, the decoration layer and the mask layer I got a face plate.

<< Formation of first transparent electrode pattern >>
<Formation of transparent electrode layer>
The front plate on which the decorative layer and the mask layer are formed is introduced into a vacuum chamber, and an ITO target (indium: tin = 95: 5 (molar ratio)) having a SnO ₂ content of 10% by mass is used. An ITO thin film having a thickness of 40 nm was formed by magnetron sputtering (conditions: base temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa) to obtain a front plate on which a transparent electrode layer was formed. The surface resistance of the ITO thin film was 80 Ω / □.

<Preparation of Coating Liquid for Photocurable Resin Layer for Etching>
A coating solution for a photocurable resin layer for etching shown below: Formulation E1 was prepared.

(Coating fluid for photo-curable resin layer for etching: prescription E1)
Methyl methacrylate / styrene / methacrylic acid copolymer (copolymer composition (mass%): 31/40/29, weight average molecular weight 60000,
Acid value: 163 mg KOH / g: 16 parts by mass Monomer 1 (trade name: BPE-500, Shin-Nakamura Chemical Co., Ltd. product): 5.6 parts by mass 0.5 mol of tetraethylene oxide monomethacrylate of hexamethylene diisocyanate added Substance: 7 parts by mass · Cyclohexanedimethanol monoacrylate as a compound having one polymerizable group in the molecule: 2.8 parts by mass · 2-chloro-N-butylacridone: 0.42 parts by mass · 2, 2 -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole: 2.17 parts by mass, leuco crystal violet: 0.26 parts by mass, phenothiazine: 0.013 parts by mass, surfactant (Product name: Megafuck F-780F, Dainippon Inn Co., Ltd.)
: 0.03 parts by mass · methyl ethyl ketone: 40 parts by mass · 1-methoxy-2-propanol: 20 parts by mass

<Formation of first transparent electrode pattern>
The front plate on which the decorative layer, the mask layer, and the transparent electrode layer were formed was washed and dried in the same manner as the formation of the mask layer. The front plate was inserted into the silicone resin stain prevention plate 13 shown in FIG. 10, and the silicone resin stain prevention plug 14 shown in FIG. 11 was inserted into the opening (15 mm Φ) of the front plate. Next, the front plate edge and the stain prevention plate, and the opening edge and the inside of the prevention plug were not soiled. Further, the adjustment was performed so that the surface of the front plate, the surface of the antifouling plate 13 and the surface of the antifouling plug 14 become flat.
Coating solution for photo-curable resin layer for the above etching with a coater for glass substrate having slit-like nozzles (product name: MH-1600, manufactured by FF Japan, Ltd.): Substrate). Subsequently, after partially drying the solvent with a VCD (vacuum drying device, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to remove the fluidity of the coating layer, the periphery of the substrate is treated with EBR (edge bead remover) The unnecessary coating solution was removed and prebaked at 120 ° C. for 3 minutes to obtain a photocurable resin layer for etching having a film thickness of 2.0 μm on the tempered glass (liquid resist method).
Exposure mask surface and etching with the substrate and exposure mask (quartz exposure mask with frame pattern) vertically standing by a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp The distance between the photocurable resin layers was set to 200 μm, and pattern exposure was performed with an exposure amount of 200 mJ / cm ² from the side of the photocurable resin layer for etching.
The front plate was removed from the antifouling plate 13 and the antifouling plug 14 made of silicone resin was removed from the opening (15 mm diameter) of the substrate.
Next, using a triethanolamine-based developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (Fujifilm Co., Ltd. product) diluted 10-fold with pure water) at 25 ° C. Development was carried out for 100 seconds, and washing was carried out at 33 ° C. for 20 seconds using a surfactant-containing washing solution (trade name: T-SD3 (manufactured by Fujifilm Corporation) diluted 10-fold with pure water). Next, the front plate was rubbed with a rotating brush, and the residue was removed by injecting pure water from an extra-high pressure cleaning nozzle. Furthermore, the post-baking process for 30 minutes and 130 degreeC was performed, and the front plate in which the decoration layer, the mask layer, the transparent electrode layer, and the photocurable resin layer pattern for etching were formed was obtained.

The front plate on which the decorative layer, the mask layer, the transparent electrode layer and the photocurable resin layer pattern for etching are formed is immersed in an etching bath containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.) Process (etching process) for 100 seconds, dissolve and remove the transparent electrode layer in the exposed area not covered with the photo-curable resin layer for etching, and attach the decorative layer, mask layer, photo-curable resin layer pattern for etching A front plate with a transparent electrode layer pattern was obtained.

Next, the front plate with a transparent electrode layer pattern with a photocurable resin layer pattern for etching was exposed to a resist stripping solution (N-methyl-2-pyrrolidone, monoethanolamine, surfactant (trade name: SURFYNOL 465) ), Dipped in a resist stripping bath containing 45 ° C. of air products, treated (peeling treatment) for 200 seconds, the photocurable resin layer for etching is removed, a decorative layer, a mask layer, A first transparent electrode pattern disposed as shown in FIG. 1 is formed across both areas of one surface of the front plate and a surface opposite to the surface of the mask layer opposite to the front plate. I got the front plate.

<< Formation of insulating layer >>
Preparation of Coating Solution for Forming Insulating Layer
Coating solution for forming an insulating layer shown below: Formulation W1 was prepared.

(Coating liquid for insulating layer formation: prescription W1)
· Binder 3 (glycidyl methacrylate adduct of cyclohexyl methacrylate (a) / methyl methacrylate (b) / methacrylic acid copolymer (c) (d) (composition (% by mass): a / b / c / d = 46/1 / 10/43, weight average molecular weight: 36000, acid value 66 mg KOH / g) 1-methoxy-2-propanol, methyl ethyl ketone solution (solid content: 45%)): 12.5 parts by mass · DPHA (dipentaerythritol hexaacrylate) Propylene glycol monomethyl ether acetate solution (76% by mass) manufactured by Nippon Kayaku Co., Ltd.
1.4 parts by mass Urethane-based monomer (trade name: NK oligo UA-32P, Shin-Nakamura Chemical Co., Ltd. product: non-volatile matter 75%, propylene glycol monomethyl ether acetate: 25%): 0.68 parts by mass tri Pentaerythritol octaacrylate (trade name: V # 802,
Osaka Organic Chemical Industry Co., Ltd .: 1.8 parts by mass Diethylthioxanthone: 0.17 parts by mass 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1-
[4- (4-morpholinyl) phenyl] -1-butanone (trade name: Irgacure 379, manufactured by BASF): 0.17 parts by mass, dispersant (trade name: Solsperse 20000, manufactured by Avicia): 0.19 parts by mass, interface Activator (trade name: Megafuck F-780F, made by Dainippon Ink)
: 0.05 parts by mass · methyl ethyl ketone: 23.3 parts by mass · MMPGAc (propylene glycol monomethyl ether acetate, manufactured by Daicel Chemical Industries, Ltd.): 59.8 parts by mass In addition, coating liquid for forming an insulating layer: solvent removal of formulation W1 The subsequent viscosity at 100 ° C. was 4000 Pa · sec.

In the same manner as the formation of the photocurable resin layer for etching, a photocurable resin layer for an insulating layer having a thickness of 1.4 μm was formed on the front plate.
Subsequently, the distance between the exposure mask (quartz exposure mask having a pattern for insulating layer) surface and the insulating layer was set to 100 μm, and pattern exposure was performed with an exposure amount of 150 mJ / cm ² (i line).

Next, using a sodium carbonate / sodium hydrogencarbonate developer (trade name: T-CD1 (Fujifilm Co., Ltd.) diluted 5 times with pure water), development was carried out at 25 ° C. for 50 seconds. Using a surfactant-containing washing solution (trade name: T-SD3 (manufactured by Fujifilm Corporation) diluted 10-fold with pure water), washing was performed at 33 ° C. for 20 seconds. Next, the front plate was rubbed with a rotating brush, and the residue was removed by injecting pure water from an extra-high pressure cleaning nozzle. Further, post-baking treatment was carried out at 230 ° C. for 60 minutes to obtain a front plate on which a decorative layer, a mask layer, a first transparent electrode pattern, and an insulating layer pattern were formed.

<< Formation of Second Transparent Electrode Pattern >>
<Formation of transparent electrode layer>
Similar to the formation of the first transparent electrode pattern, the front plate on which the decorative layer, the mask layer, the first transparent electrode pattern, and the insulating layer pattern are formed is subjected to DC magnetron sputtering treatment (conditions: temperature of substrate) An ITO thin film with a thickness of 80 nm was formed at 50 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), and a decorative layer, a mask layer, a first transparent electrode pattern, an insulating layer pattern, and a transparent electrode layer were formed. I got the front plate. The surface resistance of the ITO thin film was 110 Ω / □.

A coating solution for a photocurable resin layer for etching in the same manner as the formation of the first transparent electrode pattern: using a prescription E1, a decorative layer, a mask layer, a first transparent electrode pattern, an insulating layer pattern, a transparent electrode A front plate having a layer and a photocurable resin layer pattern for etching formed thereon was obtained (post-baking treatment; 130 ° C., 30 minutes).
Furthermore, in the same manner as the formation of the first transparent electrode pattern, the etching layer (30 ° C., 50 seconds) is removed to remove the photocurable resin layer for etching (45 ° C., 200 seconds), thereby forming a decorative layer, The mask layer, the first transparent electrode pattern, the insulating layer pattern, one surface of the front plate and the opposite surface of the surface of the mask layer opposite to the front plate as shown in FIG. The front plate which formed the 2nd transparent electrode pattern installed in was obtained.

<< Formation of conductive element different from the first and second transparent electrode patterns >>
Similarly to the formation of the first and second transparent electrode patterns, a front plate on which a decorative layer, a mask layer, a first transparent electrode pattern, an insulating layer pattern, and a second transparent electrode pattern are formed is used as a DC magnetron Sputtering was performed to obtain a front plate on which a 200 nm-thick aluminum (Al) thin film was formed.

Coating liquid for photocurable resin layer: using the prescription E1 in the same manner as the formation of the first and second transparent electrode patterns: a decorative layer, a mask layer, a first transparent electrode pattern, and an insulating layer pattern A front plate on which a second transparent electrode pattern, an aluminum thin film, and a photocurable resin layer pattern for etching were formed was obtained (post-baking treatment; 130 ° C., 30 minutes).
Furthermore, in the same manner as the formation of the first transparent electrode pattern, the etching layer (30 ° C., 50 seconds) is removed to remove the photocurable resin layer for etching (45 ° C., 200 seconds), thereby forming a decorative layer, A front plate on which a conductive element different from the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns was formed was obtained.

<< Formation of transparent protective layer >>
In the same manner as in the formation of the insulating layer, the coating liquid for forming the insulating layer: Formulation W1 is applied to the front plate on which the conductive elements other than the first and second transparent electrode patterns are formed, dried, and exposed The entire surface is exposed with an exposure dose of 200 mJ / cm ² (i-line) without a mask, developed, post-exposed (1000 mJ / cm ² ), post-baked, and then the decorative layer, mask layer, first transparent electrode An insulating layer (transparent protective layer) was laminated as shown in FIG. 1 so as to cover all of the conductive elements other than the pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns. The front plate 1 was obtained. The obtained front plate 1 was used as a capacitive input device of Example 1.

<< Production of Image Display Device (Touch Panel) >>
The liquid crystal display device manufactured by the method described in JP-A-2009-47936 is bonded to the front plate 1 (electrostatic capacitance type input device of Example 1) manufactured earlier, and the electrostatic capacitance type input is performed by a known method. The image display apparatus 1 of Example 1 provided with an apparatus as a component was produced.

<< Overall Evaluation of Front Plate 1 and Image Display Device 1 >>
In each of the above-described steps, a conductive element different from the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns is formed The front plate 1 (the capacitance-type input device of Example 1) had no dirt on the opening and the back surface, was easy to clean, and had no problem of contamination of other members.
Moreover, there were no pinholes in the decorative layer, and there were no problems with whiteness and unevenness. Similarly, the mask layer had no pinholes and was excellent in light shielding properties.
And there is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and the conductive element different from them, while the first transparent electrode pattern and the second transparent electrode pattern It had insulation between the transparent electrode patterns.
Furthermore, the transparent protective layer was free from defects such as air bubbles, and an image display device excellent in display characteristics was obtained.

Example 2
<Preparation of Coating Liquid for Forming Conductive Decorative Layer>
(Preparation of Silver Nanowire Dispersion (1))
A silver nitrate solution was prepared by dissolving 0.51 g of silver nitrate powder in 50 mL of pure water. Thereafter, 1N ammonia water was added to the silver nitrate solution until it became transparent, and pure water was added so that the total amount would be 100 mL, to prepare an additive solution A.
Further, 0.5 g of glucose powder was dissolved in 140 mL of pure water to prepare an additive solution G.
Further, 0.5 g of HTAB (hexadecyl-trimethyl ammonium bromide) powder was dissolved in 27.5 mL of pure water to prepare an additive solution H.

Next, 20.6 mL of the additive solution A was placed in a three-necked flask and stirred at room temperature. Add 41 mL of pure water, 20.6 mL of Additive Solution H, and 16.5 mL of Additive Solution G to this solution in the order of a funnel, and heat at 90 ° C for 5 hours with stirring at 200 rpm for 5 hours. I got (1).
After cooling the obtained silver nanowire water dispersion (1), while stirring, polyvinyl pyrrolidone (trade name: K-30, manufactured by Wako Pure Chemical Industries, Ltd.) was used in an amount of 0.05 to 1 mass of silver. It added so that it might become. The resulting solution was then centrifuged and purified to a conductivity of 50 μS / cm or less. Furthermore, propylene glycol monomethyl ether was added and centrifugation was performed. Next, water was removed, and finally propylene glycol monomethyl ether was added to prepare silver nanowire solvent dispersion (1) (silver nanowire dispersion (1)).

(Preparation of Coating Solution for Forming Conductive Decorative Layer)
The following composition was stirred, and mixed with the silver nanowire dispersion (1) such that the final silver concentration was 1.0% by mass, to prepare a coating liquid C1 for forming a conductive decorative layer.

-Composition of Coating Solution C1 for Forming Conductive Decorative Layer-
The binder 3 (solid content: 45%): 3.80 parts by mass KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.): 1.59 parts by mass 2- (dimethylamino) -2-[(4-methyl) Phenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: Irgacure 379, manufactured by BASF): 0.159 parts by mass EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.): 0 .150 parts by weight of surfactant (trade name: Megafac F-781F, manufactured by Dainippon Ink)
0.002 parts by mass MMPGAc (propylene glycol monomethyl ether acetate, manufactured by Daicel Chemical Industries, Ltd.): 19.3 parts by mass

<< Formation of Transparent Electrode Pattern, Insulating Layer, etc. >>
After obtaining a front plate on which a decorative layer and a mask layer are formed in the same manner as in Example 1, a coating solution for a photocurable resin layer for etching: instead of prescription E1, a coating for forming a conductive decorative layer Using the liquid C1, the conductive decorative layer was laminated in the following procedure to form a first transparent electrode pattern.
First, the front plate on which the decorative layer and the mask layer are formed is washed, and a coating solution C1 for forming a conductive decorative layer is applied to a coater for glass substrate having a slit-like nozzle on the mask layer side of the front plate. -It applied by S Japan company make and brand name: MH-1600), and it dried, and obtained the conductive decoration layer with a film thickness of 2.0 micrometers. The distance between an exposure mask (a quartz exposure mask having a transparent electrode pattern) surface and the conductive decorative layer was set to 100 μm, and pattern exposure was performed with an exposure dose of 100 mJ / cm ² (i line).
Next, using a sodium carbonate / sodium hydrogencarbonate developer (trade name: T-CD1 (Fujifilm Co., Ltd.) diluted 5 times with pure water), development was carried out at 25 ° C. for 60 seconds. Using a surfactant-containing washing solution (trade name: T-SD3 (manufactured by Fujifilm Corporation) diluted 10-fold with pure water), washing was performed at 33 ° C. for 20 seconds. Next, the front plate was rubbed with a rotating brush, and the residue was removed by injecting pure water from an extra-high pressure cleaning nozzle. Further, post-baking treatment was performed at 230 ° C. for 60 minutes to obtain a front plate on which a mask layer and a first transparent electrode pattern were formed.

Subsequently, in the same manner as in Example 1, an insulating layer was formed. Subsequently, the conductive decorative layer was laminated in the same manner as in the formation of the first transparent electrode pattern in the second embodiment to form a second transparent electrode pattern. Furthermore, in the same manner as in Example 1, a conductive element different from the first and second transparent electrode patterns and a transparent protective layer were formed to obtain a front plate 2. This was used as a capacitive input device of Example 2.
Further, in the same manner as in Example 1, an image display apparatus 2 of Example 2 was produced.

<< Evaluation of front panel 2 and image display device 2 >>
In each of the above-described steps, a conductive element different from the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns is formed The front plate 2 had no dirt on the opening and the back, was easy to clean, and had no problem of contamination of other members.
In addition, the mask layer had no pinholes and was excellent in light shielding properties.
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and the other conductive element, and while the first transparent electrode pattern and the second transparent electrode pattern do not have any problem. It had insulation between the transparent electrode patterns.
Furthermore, the transparent protective layer was free from defects such as air bubbles, and an image display device excellent in display characteristics was obtained.

[Examples 3 to 10]
Silicone resin KR-300 (Example 3), Silicone resin KR-282 (Example 4) in place of silicone resin KR-311 in preparation of the coloring composition for heat resistance decoration (formulation L1) of Example 1 Mixture of silicone resin KR-300 and silicone resin KR-282 (Example 5), silicone resin KR-271 (Example 6), silicone resin KR-255 (Example 7), silicone resin KR- The heat resistant decorative coloring composition (formulation L1) of Example 1 except that 212 (Example 8), silicone resin KR-9706 (Example 9), and silicone resin KR-5230 (Example 10) were used. In the same manner as in the preparation (the solid content addition amount is the same), the heat resistant decorative coloring compositions of Examples 3 to 10 (respectively formulated as L3 to L10) were prepared .
The heat resistant decorative coloring composition of Examples 3 to 10 was used instead of the heat resistant decorative coloring composition used in Example 1, that is, Example 1 except using the binder shown in Table 1 below. In the same manner as in the above, a front plate having a decorative layer formed was produced. The evaluation results of the obtained front plate are shown in Table 1 below. Thereafter, in the same manner as in Example 1, a conductive layer different from the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns And the front plates 3 to 10 which are the capacitance type input devices of Examples 3 to 10 in which the transparent protective layer is formed, and the image display devices 3 to 10 each having the capacitance type input device as a component.
For the front plates 3 to 10, the brightness, the whiteness, the reticulation, the yield, the adhesion of the decorative layer, the contamination of the opening, and the omission of the opening were at practical levels.
In addition, the mask layer had no pinholes and was excellent in light shielding properties.
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and the other conductive element, and while the first transparent electrode pattern and the second transparent electrode pattern do not have any problem. It had insulation between the transparent electrode patterns.
Furthermore, the transparent protective layer was free from defects such as air bubbles, and an image display device excellent in display characteristics was obtained.

[Examples 11 to 13]
Titanium oxide CR-97 (alumina / zirconia-treated rutile type, primary particle diameter 0) manufactured by Ishihara Sangyo Co., Ltd. used in the preparation of the white pigment dispersion 1 used for the heat resistant decorative coloring composition (formulation L5) of Example 5 Instead of Ishihara Sangyo CR-60 (alumina treated rutile type, primary particle diameter 0.21 μm, Example 11), Ishihara Sangyo CR-50 (alumina treated rutile type, primary particle diameter 0. Preparation of the coloring composition for heat-resistant decoration of Example 5 except using 25 μm, Example 12), CR-58 (alumina-treated rutile type, primary particle diameter 0.28 μm, Example 13) manufactured by Ishihara Sangyo Co., Ltd. Similarly, the heat-resistant and decorative coloring compositions of Examples 11 to 13 (respectively referred to as Formulations L11 to L13) were prepared.
A decorative layer is formed in the same manner as in Example 5 except that the heat resistant decorative coloring composition of Examples 11 to 13 is used instead of the heat resistant decorative coloring composition used in Example 5. The front plate was made. The evaluation results of the obtained front plate are shown in Table 1 below. Thereafter, in the same manner as in Example 5, a conductive layer different from the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns And, the front plates 11 to 13 which are the capacitance type input devices of Examples 11 to 13 in which the transparent protective layer is formed, and the image display devices 11 to 13 each having the capacitance type input device as a component are manufactured.
The front plates 11 to 13 had no problem in the contamination of the opening and the back surface, were easy to clean, and had no problem of contamination of other members.
In addition, the mask layer had no pinholes and was excellent in light shielding properties.
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and the other conductive element, and while the first transparent electrode pattern and the second transparent electrode pattern do not have any problem. It had insulation between the transparent electrode patterns.
Furthermore, the transparent protective layer was free from defects such as air bubbles, and an image display device excellent in display characteristics was obtained.

[Examples 14 to 19]
The titanium oxide content relative to 44 parts by mass of the total solid content by mass of the heat-resistant decorative coloring composition (formulation L5) of Example 5 is replaced with 20 parts by mass (Example 14) and 26 respectively. Example except changing into mass part (Example 15), 32 mass parts (Example 16), 36 mass parts (Example 17), 60 mass parts (Example 18), 75 mass parts (Example 19) In the same manner as in the preparation of the heat resistant decorative coloring composition of No. 5, the heat resistant decorative coloring compositions of Examples 14 to 19 (respectively referred to as Formulations L14 to L19) were prepared.
A decorative layer is formed in the same manner as in Example 5 except that the heat resistant decorative coloring composition of Examples 14 to 19 is used instead of the heat resistant decorative coloring composition used in Example 5. The front plate was made. The evaluation results of the obtained front plate are shown in Table 1 below. Thereafter, in the same manner as in Example 5, a conductive layer different from the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns Examples 14 to 19 in which a transparent protective layer was formed The front plates 14 to 19 which are capacitance type input devices, and the image display devices 14 to 19 including the capacitance type input devices as components were manufactured.
From the results of Table 1 below, all evaluations were at practical levels within the range of 20 parts by mass to 75 parts by mass. More specifically, as the titanium oxide content increases from 20 parts by mass to 75 parts by mass, the yield, the adhesion to the decorative layer, and the missing part of the opening slightly decrease, but it is a practical level, and the whiteness and reticulation And the dirt at the opening tended to improve. The lightness of 38 parts by mass to 60 parts by mass was the most favorable region.
In addition, the mask layer had no pinholes and was excellent in light shielding properties.
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and the other conductive element, and while the first transparent electrode pattern and the second transparent electrode pattern do not have any problem. It had insulation between the transparent electrode patterns.
Furthermore, the transparent protective layer was free from defects such as air bubbles, and an image display device excellent in display characteristics was obtained.

[Examples 20 to 22]
In the preparation of the heat-resistant decorative coloring composition (formulation L5) of Example 5, the phosphoric acid-based antioxidant IRGAFOS 168 (manufactured by BASF Japan Ltd., Example) is used in place of the phosphoric acid / hindered phenol-based antioxidant Antimulsifier GP. 20) The heat resistance of Example 5 except that phosphoric acid based antioxidant IRGAFOS 38 (manufactured by BASF Japan Ltd., Example 21) and phosphoric acid / hindered phenolic antioxidant IRGAMOD 295 (manufactured by BASF Japan Ltd., Example 22) were used. In the same manner as in the preparation of the coloring composition for decorative decoration (formulation L5), the coloring composition for heat-resistant decoration of Examples 20 to 22 (respectively referred to as formulation L20 to L22) was prepared.
A decorative layer is formed in the same manner as in Example 5 except that the heat resistant decorative coloring composition of Examples 20 to 22 is used instead of the heat resistant decorative coloring composition used in Example 5. The front plate was made. The evaluation results of the obtained front plate are listed in Table 2 below. Thereafter, in the same manner as in Example 5, a conductive layer different from the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns Also, the front plates 20 to 22 which are the capacitance type input devices of Examples 20 to 22 in which the transparent protective layer is formed, and the image display devices 20 to 22 each having the capacitance type input device as a component are manufactured.
The front plates 20 and 21 slightly improved the whiteness with respect to the front plate 5, and the others were equal and practical.
The evaluation results of the front plate 22 were the same as those of the front plate 5 and were at the same practical level.

[Examples 23 and 24]
In Example 5, instead of setting the thickness of the formed decorative layer to 36 μm (Example 5; 6 times printing application), 18 μm (Example 23; 3 times printing application) or 42 μm (Example 24; 7) A front plate on which a decorative layer was formed was produced in the same manner as in Example 5 except that the decorative layers of Examples 23 and 24 were formed as the single-step printing application). The evaluation results of the obtained front plate are listed in Table 2 below. Thereafter, in the same manner as in Example 5, a conductive layer different from the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns And the front plates 23 and 24 which are the capacitance type input devices of Examples 23 and 24 in which the transparent protective layer is formed, and the image display device 23 provided with the capacitance type input device as a component.
With respect to the front plate 5, the front plates 23 and 24 had practical levels of brightness, whiteness, yield, reticulation, decorative layer adhesion, opening contamination and opening loss.
The front plates 23 and 24 had no problem in the contamination of the opening and the back surface, were easy to clean, and did not have the problem of contamination of other members.
In addition, the mask layer had no pinholes and was excellent in light shielding properties.
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and the other conductive element, and while the first transparent electrode pattern and the second transparent electrode pattern do not have any problem. It had insulation between the transparent electrode patterns.
Furthermore, the transparent protective layer was free from defects such as air bubbles, and an image display device excellent in display characteristics was obtained.

[Example 25]
In the preparation of the coloring composition for heat resistance decoration (formulation L20) of Example 20, it replaces with a solid equivalent mixture of silicone resin KR-300 and silicone resin KR-282, and adds total solid content of silicone resin The heat-resistant and decorative coloring composition of Example 20 (Formulation L 20) except that a 1: 1 equivalent mixture of silicone resin KR-300 and silicone resin KR-311 (Example 25) was used without change. In the same manner as in the preparation of (1), a heat-resistant decorative coloring composition (referred to as formulation L25) was prepared, and it was used as the heat-resistant decorative coloring composition of Example 25.
A front plate on which a decorative layer was formed was produced in the same manner as in Example 20 except that the coloring composition for heat resistance decoration (Formulation L 25) of Example 25 was used, that is, it was changed to the binder shown in Table 2 below. . The evaluation results of the obtained front plate are listed in Table 2 below. Thereafter, in the same manner as in Example 20, a conductive layer different from the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns Also, a front plate 25 which is a capacitance type input device of Example 25 in which a transparent protective layer is formed, and an image display device 25 provided with the capacitance type input device as a component are manufactured.
Although the front plate 25 has reduced whiteness, adhesion to the decorative layer, stains on the opening, and loss of the opening relative to the front plate 20, it is at a practical level, and the evaluation results of lightness and yield reticulation It was equal and practical.
The front plate 25 had no problem in the contamination of the opening and the back surface, was easy to clean, and had no problem of contamination of other members.
In addition, the mask layer had no pinholes and was excellent in light shielding properties.
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and the other conductive element, and while the first transparent electrode pattern and the second transparent electrode pattern do not have any problem. It had insulation between the transparent electrode patterns.
Furthermore, the transparent protective layer was free from defects such as air bubbles, and an image display device excellent in display characteristics was obtained.

[Example 26]
In the preparation of the coloring composition for heat resistance decoration (formulation L25) of Example 25, a zinc-based condensation catalyst D-15 (manufactured by Shin-Etsu Chemical Co., Ltd.) is added to the coloring composition for heat resistance decoration (formulation L25) 4% by mass of the total solid content addition amount of the resin was added to prepare a heat-resistant and decorative colored composition of Example 26 (referred to as Formulation L26).
A decorative layer is prepared in the same manner as in Example 25 except that the heat resistant decorative coloring composition of Example 26 is used instead of the heat resistant decorative coloring composition (Formulation L 25) used in Example 25. A front plate was formed. The evaluation results of the obtained front plate are listed in Table 2 below. Thereafter, in the same manner as in Example 25, a conductive layer different from the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns Also, a front plate 26 which is a capacitance-type input device of Example 26 in which a transparent protective layer is formed, and an image display device 26 provided with the capacitance-type input device as a component are manufactured.
Although the front plate 26 has reduced whiteness, adhesion to the decorative layer, stains on the opening, and missing openings with respect to the front plate 25, it is at a practical level, and evaluation results of lightness and yield reticulation It was equal and practical.
In addition, the mask layer had no pinholes and was excellent in light shielding properties.
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and the other conductive element, and while the first transparent electrode pattern and the second transparent electrode pattern do not have any problem. It had insulation between the transparent electrode patterns.
Furthermore, the transparent protective layer was free from defects such as air bubbles, and an image display device excellent in display characteristics was obtained.

[Examples 27 and 28]
In the preparation of the heat-resistant and decorative coloring composition (formulation L26) of Example 26, the solid content ratio of silicone resin KR-300 to silicone resin KR-311 is changed to 1/1 (Example 26). (Silicone resin) in the same manner as in the preparation of the coloring composition for heat-resistant decoration (formulation L26) of Example 26 except that 3/7 (Example 27) and 7/3 (Example 28), respectively. The heat-resistant and decorative coloring compositions of Examples 27 and 28 (the formulations L27 and L28, respectively) were prepared.
A decorative layer is formed in the same manner as in Example 26 except that the heat resistant decorative coloring composition of Examples 27 and 28 is used instead of the heat resistant decorative coloring composition used in Example 26. The front plate was made. The evaluation results of the obtained front plate are listed in Table 2 below. Thereafter, in the same manner as in Example 26, a conductive layer different from the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns In addition, front panels 27 and 28, which are the capacitance type input devices of Examples 27 and 28 in which the transparent protective layer is formed, and image display devices 27 and 28 each including the capacitance type input device as a component, are manufactured.
The front plates 27 and 28 had practical levels of lightness, whiteness, reticulation, yield, adhesion of the decorative layer, contamination of the opening, and missing of the opening.
In addition, the mask layer had no pinholes and was excellent in light shielding properties.
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and the other conductive element, and while the first transparent electrode pattern and the second transparent electrode pattern do not have any problem. It had insulation between the transparent electrode patterns.
Furthermore, the transparent protective layer was free from defects such as air bubbles, and an image display device excellent in display characteristics was obtained.

[Examples 29 to 33]
In the preparation of the coloring composition for heat resistance decoration (formulation L26) of Example 26, the silicone resin KR is replaced with an equivalent mixture of solid content 1/1 of silicone resin KR-300 and silicone resin KR-311, respectively. -400 (Example 29), silicone resin KR-500 (Example 30), solid ratio of silicone resin KR-400 and silicone resin KR-500 = 3/7 (Example 31), silicone resin KR-400 Solid content ratio of silicone resin KR-500 = 7/3 (Example 32), solid ratio of silicone resin KR-400, silicone resin KR-500, and silicone alkoxy oligomer X-40-9225 = 70/30/2. Example 26 was carried out in the same manner as Example 26 except that 5 (Example 33) was used. Flip.), Heat resistance decorative coloring composition for Examples 29 to 33 (respectively identified as Formulation L29 ~ L33) was prepared.
A decorative layer is prepared in the same manner as in Example 26 except that the heat resistant decorative coloring compositions of Examples 29 to 33 are used instead of the heat resistant decorative coloring composition used in Example 26. The formed front plate was produced. The evaluation results of the obtained front plate are listed in Table 2 below. Thereafter, in the same manner as in Example 26, a conductive layer different from the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns Also, the front plates 29 to 33, which are the capacitance type input devices of Examples 29 to 33 in which the transparent protective layer is formed, and the image display devices 29 to 33 provided with the capacitance type input device as components are manufactured.
In the front plates 29 to 33, the brightness, the whiteness, the reticulation, the yield, the adhesion of the decorative layer, the contamination of the opening, and the omission of the opening were at practical levels.
In addition, the mask layer had no pinholes and was excellent in light shielding properties.
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and the other conductive element, and while the first transparent electrode pattern and the second transparent electrode pattern do not have any problem. It had insulation between the transparent electrode patterns.
Furthermore, the transparent protective layer was free from defects such as air bubbles, and an image display device excellent in display characteristics was obtained.

[Examples 34 to 39]
In the preparation of the coloring composition for heat resistance decoration (formulation L26) of Example 26, replacing with an equivalent mixture of solid content 1/1 of silicone resin KR-300 and silicone resin KR-311, respectively, silicone resin For the type, a toluene solution of the condensate of Synthesis Example 1 (Example 34; methyl tolyl type silicone resin), a toluene solution of the condensate of Synthesis Example 2 (Example 35; methyl benzyl type silicone resin), Synthesis Example 3 Solution of the condensate of the present invention (Example 36; methyl cumyl type silicone resin), toluene solution of the condensate of the synthesis example 4 (Example 37; ethyl tolyl type silicone resin), toluene solution of the condensate of the synthesis example 5 (Example 38; propyl / tolyl type silicone resin), a toluene solution of the condensation product of Synthesis Example 6 (Example 39; methyl hydride type silicone resin) The heat-resistant and decorative coloring composition of each of Examples 34 to 39 (respectively formulated L 34 to L) in the same manner as Example 26 (the total solid content addition amount of the silicone resin is the same) except using corn resin). L39 was prepared.
A decorative layer is prepared in the same manner as in Example 26 except that the heat resistant decorative coloring composition of Examples 34 to 39 is used instead of the heat resistant decorative coloring composition used in Example 26. The formed front plate was produced. The evaluation results of the obtained front plate are listed in Table 2 below. Thereafter, in the same manner as in Example 26, a conductive layer different from the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns And the front plates 34 to 39 which are the capacitance type input devices of Examples 34 to 39 in which the transparent protective layer is formed, and the image display devices 34 to 39 having the capacitance type input device as a component.
For the front plates 34 to 39, the brightness, the whiteness, the reticulation, the yield, the adhesion of the decorative layer, the contamination of the opening, and the omission of the opening were at practical levels.
In addition, the mask layer had no pinholes and was excellent in light shielding properties.
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and the other conductive element, and while the first transparent electrode pattern and the second transparent electrode pattern do not have any problem. It had insulation between the transparent electrode patterns.
Furthermore, the transparent protective layer was free from defects such as air bubbles, and an image display device excellent in display characteristics was obtained.

[Examples 40 and 41]
In preparation of the coloring composition for heat resistance decoration (formulation L1) of Example 1, solid content 9/1 of silicone resin KR-251 (Example 40) and silicone resin KR-251 and X-40-9246, respectively. (The silicone resin was prepared in the same manner as in Example 1 except that the heat resistant decorative coloring composition (Formulations L40 and L41) was changed to the mixture of Examples (Example 41), that is, it was changed to the binder shown in Table 2 below. The total solid content addition amount was the same.), And the heat resistant and decorative coloring composition of Examples 40 and 41 (respectively formulated as L40 and L41) were prepared.
A decorative layer was formed in the same manner as in Example 1 except that the heat resistant decorative coloring compositions of Examples 40 and 41 were used in place of the heat resistant decorative coloring composition of Example 1, respectively. A front plate was produced. The evaluation results of the obtained front plate are listed in Table 2 below. Thereafter, in the same manner as in Example 1, a conductive layer different from the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns And the front plates 40 and 41 which are the capacitance-type input devices of Examples 40 and 41 which formed the transparent protective layer, The image display devices 40 and 41 provided with the capacitance-type input device as a component were produced.
With respect to the front plate 1, the front plates 40 and 41 have significantly improved lightness, and the whiteness, reticulation, yield, adhesion of the decorative layer, the contamination of the opening, and the omission of the opening were at practical levels.
In addition, the mask layer had no pinholes and was excellent in light shielding properties.
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and the other conductive element, and while the first transparent electrode pattern and the second transparent electrode pattern do not have any problem. It had insulation between the transparent electrode patterns.
Furthermore, the transparent protective layer was free from defects such as air bubbles, and an image display device excellent in display characteristics was obtained.

Comparative Example 1
In preparation of the coloring composition for heat resistance decoration (formulation L1) of Example 1, it replaces with silicone resin KR-311 and adds the same solid content of the following polyamic acid (it describes as a polyimide in following Table 2). A heat resistant decorative coloring composition (Formulation L51) was prepared in the same manner as in the preparation of the heat resistant decorative coloring composition of Example 1 except for the use. The obtained heat resistant decorative coloring composition was used as the heat resistant decorative coloring composition of Comparative Example 1.

(Polymerization of Polyimide Precursor Polyamide Acid)
After adding 210 parts by mass of 4,4'-methylenebis (cyclohexylamine) to a reaction vessel and dissolving it in 2860 parts by mass of N-methyl-2-pyrrolidone, the reaction mixture was stirred under nitrogen flow with stirring of pyromellitic dianhydride there. A clear and viscous polyamic acid solution was obtained by gradually adding 218 parts by weight of powder and reacting at 35 ° C. for 8 hours.

A tempered glass is prepared in the same manner as in Example 1 except that the coloring composition for heat resistance decoration (Formulation L51) of Comparative Example 1 is used instead of the coloring composition for heat resistance decoration used in Example 1. A front plate 51 having a decorative layer formed thereon was formed. After post-baking the front plate 51 on which the decorative layer is formed, the temperature is raised to 350 ° C. for about 20 seconds, and heat treatment is performed at 350 ° C. for 7 minutes to complete imidization of the polyamic acid.
Thereafter, in the same manner as in Example 1, a conductive layer different from the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns And the front plate 51 which is an electrostatic capacitance type input device of the comparative example 1 which formed the transparent protective layer, and the image display apparatus 51 provided with the electrostatic capacitance type input device as a component were produced. The evaluation results of the obtained front plate 51 of Comparative Example 1 are shown in Table 2 below.
The front plate 51 had the whiteness, the adhesion to the decorative layer, the missing opening portion, and the yield significantly lowered with respect to the front plate 1, and became an NG level. There was no problem in the contamination of the opening and the back surface, it was easy to clean, and there was no problem of contamination of other members.
Further, the front plate 51 had no pinholes in the mask layer and was excellent in light shielding properties.
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and the other conductive element, and while the first transparent electrode pattern and the second transparent electrode pattern do not have any problem. It had insulation between the transparent electrode patterns.
Furthermore, the transparent protective layer was free from defects such as air bubbles, and an image display device excellent in display characteristics was obtained.

Comparative Example 2
Acrylic binder 1 (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer in place of silicone resin KR-311 in preparation of heat resistant decorative coloring composition (formulation L1) of Example 1; Comparative Example 2 in the same manner as in the preparation of the coloring composition for heat-resistant decoration of Example 1 except that the weight average molecular weight was 37,000 and the same solid content was added and used in Table 2 below. The heat resistant decorative coloring composition (formulation L52) was prepared.
A decorative layer is prepared in the same manner as in Example 1, except that the heat resistant decorative coloring composition (Formulation L52) of Comparative Example 2 is used instead of the heat resistant decorative coloring composition used in Example 1. Comparative Example 2 in which the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, the conductive element different from the first and second transparent electrode patterns, and the transparent protective layer are formed A front plate 52, which is a capacitive input device, and an image display device 52 provided with a capacitive input device as components were manufactured. The evaluation results of the front plate 52 of Comparative Example 2 obtained are shown in Table 2 below.
The front plate 52 had the whiteness, the adhesion to the decorative layer, the missing opening portion, and the yield significantly lower than that of the front plate 1 and became an NG level. There was no problem in the contamination of the opening and the back surface, it was easy to clean, and there was no problem of contamination of other members.
Further, the front plate 52 had no pinholes in the mask layer and was excellent in light shielding properties.
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and the other conductive element, and while the first transparent electrode pattern and the second transparent electrode pattern do not have any problem. It had insulation between the transparent electrode patterns.
Furthermore, the transparent protective layer was free from defects such as air bubbles, and an image display device excellent in display characteristics was obtained.

From the above Table 1 and Table 2, by using the heat-resistant decorative coloring composition of the present invention, a white decorative layer having good lightness, whiteness, reticulation and adhesion after transfer can be obtained with high quality. It turns out that it can be obtained at a rate.
Further, as described above, according to the method of manufacturing the capacitance-type input device of the present invention using the coloring composition for heat-resistant decoration of the present invention, the capacitance having the merit of thinning and weight reduction The mold input device can be made high quality in a simple process. Therefore, it is understood that the capacitance type input device manufactured by the manufacturing method of the present invention and the image display device using the same have high quality.
According to a more preferable embodiment of the method of manufacturing a capacitance-type input device according to the present invention, even in the case where a substrate having an opening is used, the resist is protruded (moist) or the front plate back side (non-contact surface side) It turned out that there is little pollution.

1 front plate 1a front plate non-contact surface 2a decorative layer 2b mask layer 3 first transparent electrode pattern

3a pad portion

3b connection portion 4 second transparent electrode pattern 5 insulating layer 6 conductive element 7 transparent protective layer 8 opening Part 10 Capacitance type input device 11 Hardened glass 12 Another conductive element 13 Antifouling plate 14 Antifouling plug C First direction D Second direction

Claims

A coloring composition for heat resistant decoration comprising at least (A) a white inorganic pigment and (B) a silicone resin.
The heat-resistant decorative coloring composition according to claim 1, wherein the heat-resistant decorative coloring composition further comprises (C) an antioxidant.
3. The silicone resin according to claim 1, wherein the silicone resin (B) comprises a modified silicone resin or a straight silicone resin containing at least a siloxane structure represented by the following general formula (1) in its molecule. The heat resistant decorating coloring composition as described.

In the general formula (1), R 1 independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear or branched chain having 1 to 20 carbon atoms Or a cyclic alkyl group, a linear, branched or cyclic substituted alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms Represents a group or an aralkyl group having 7 to 20 carbon atoms.
In the general formula (1), R 1 independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms 4. The heat-resistant and decorative coloring composition according to claim 3, which is a substituted alkyl group or an aryl group having 6 to 9 carbon atoms.
In the said General formula (1), R < 1 > represents independently a hydrogen atom, a methyl group, or a tolyl group, The coloring composition for heat-resistant decoration of Claim 3 characterized by the above-mentioned.
The heat resistant additive according to any one of claims 1 to 5, wherein the content of the white inorganic pigment is 20 to 75% by mass with respect to the total solid content of the heat resistant decorative colored composition. Colored composition for decoration.
The heat-resistant decorative coloring composition according to any one of claims 1 to 6, wherein the white inorganic pigment is rutile-type titanium oxide surface-treated with an inorganic substance.
The coloring composition according to claim 7, wherein the rutile titanium oxide surface-treated with the inorganic substance is rutile titanium oxide surface-treated with at least one of alumina and zirconia. .
The heat-resistant decorative coloring composition according to any one of claims 1 to 8, wherein the heat-resistant decorative coloring composition is for electrostatic capacitance type input device front plate decoration. .
A method of manufacturing a capacitive input device comprising a front plate, and at least one of the following elements (1) and (3) to (5) on one of the surfaces of the front plate:
A heat-resistant decorative coloring composition according to any one of claims 1 to 9 is applied to one side of the front plate to form at least (1) a decorative layer. A method of manufacturing a capacitive input device.
(1) Decorative layer (3) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction through connection portions (4) The first transparent electrode pattern A plurality of second electrode patterns (5) comprising a plurality of pad portions which are electrically insulated and extend in a direction crossing the first direction (5) the first transparent electrode pattern and the second Layer that electrically isolates from the electrode pattern of
The capacitive input device is further electrically connected to (6) at least one of the first transparent electrode pattern and the second electrode pattern, and the first transparent electrode pattern and the second electrode The method of manufacturing a capacitive input device according to claim 10, further comprising a conductive element different from the pattern.
The method according to claim 10, wherein the second electrode pattern is a transparent electrode pattern.
The method for manufacturing a capacitance-type input device according to any one of claims 10 to 12, wherein the thickness of the (1) decorative layer is 1 to 40 μm.
The heat-resistant decorative coloring composition is applied to one of the surfaces of the front plate, and then heated to 180 to 300 ° C. under an environment of 0.08 to 1.2 atm, A method of manufacturing a capacitive input device according to any one of claims 10 to 13, characterized by forming a decorative layer.
The method of manufacturing a capacitive input device according to claim 14, wherein the heating is performed in an air environment.
The capacitance type according to any one of claims 10 to 15, wherein the step (1) of forming the decorative layer is performed by printing the heat resistant decorative coloring composition. Method of manufacturing an input device.
17. The method according to any one of claims 10 to 16, further comprising (2) forming a mask layer on the surface of the surface of the decorative layer opposite to the surface facing the front plate. The manufacturing method of the capacitance-type input device as described in a term.
At least one of the (3) first transparent electrode pattern and the (4) second electrode pattern is opposed to the front plate among the surface of the front plate and the surface of the (2) mask layer The method of manufacturing a capacitive input device according to claim 17, wherein the method is installed across both areas of the surface opposite to the surface.
The capacitive input device is further electrically connected to (6) at least one of the first transparent electrode pattern and the second electrode pattern, and the first transparent electrode pattern and the second electrode Have conductive elements separate from the pattern,
19. The conductive film according to claim 17 or 18, wherein the (6) another conductive element is provided on at least the surface of the (2) mask layer opposite to the surface facing the front plate. The manufacturing method of the capacitance-type input device as described.
Furthermore, a transparent protective layer is formed to cover all or part of the elements (1) and (3) to (5), and the static according to any one of claims 10 to 19 is characterized. Method of manufacturing a capacitive input device.
The method for producing a capacitance-type input device according to claim 20, wherein the transparent protective layer is formed using a curable resin composition.
The capacitive input device is further electrically connected to (6) at least one of the first transparent electrode pattern and the second electrode pattern, and the first transparent electrode pattern and the second electrode Have conductive elements separate from the pattern,
The (4) second electrode pattern is a transparent electrode pattern,
The (3) first transparent electrode pattern, the (4) second electrode pattern, and the (6) another conductive element are formed of a transparent conductive material using an etching pattern formed of a curable resin composition. The method of manufacturing a capacitance-type input device according to any one of claims 10 to 21, which is formed by performing an etching process.
The capacitive input device is further electrically connected to (6) at least one of the first transparent electrode pattern and the second electrode pattern, and the first transparent electrode pattern and the second electrode Have conductive elements separate from the pattern,
The (4) second electrode pattern is a transparent electrode pattern,
Forming at least one of the (3) first transparent electrode pattern, the (4) second electrode pattern, and the (6) another conductive element using the conductive curable resin composition The method for manufacturing a capacitance-type input device according to any one of claims 10 to 21, characterized in that
Perform surface treatment on one side of the front plate;
The method for producing a capacitive input device according to any one of claims 10 to 23, characterized in that a curable resin composition is applied on one surface of the front plate subjected to the surface treatment. .
The method for manufacturing a capacitive input device according to claim 24, wherein a silane compound is used for the surface treatment of the front plate.
The method for manufacturing a capacitive input device according to any one of claims 10 to 25, wherein the front plate has an opening at least in part.
A capacitive input device manufactured by the method of manufacturing a capacitive input device according to any one of claims 10 to 26.
An image display apparatus comprising the capacitance type input device according to claim 27 as a component.