JP5860419B2 - Coloring composition for heat-resistant decoration, method for manufacturing capacitive input device, capacitive input device, and image display device including the same - Google Patents

Description

  The present invention relates to a heat-resistant decorative coloring composition for producing a capacitive input device capable of detecting a finger contact position as a change in capacitance, a method for producing a capacitive 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, electronic devices such as mobile phones, car navigation systems, personal computers, ticket vending machines, and bank terminals have been equipped with a tablet-type input device on the surface of a liquid crystal device, etc., and an instruction image displayed in the image display area of the liquid crystal device In some cases, information corresponding to the instruction image can be input by touching a part where the instruction image is displayed with a finger or a touch pen.

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

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

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

  Furthermore, a capacitive touch panel is disclosed in which a mask layer, a sense circuit, and an interlayer insulating layer are integrally formed on the non-contact side surface of the front plate (see, for example, Patent Document 3 below). According to Patent Document 3, since the capacitive touch panel has a front plate integrated with the capacitive input device, it is possible to reduce the thickness / weight and further mask the sense circuit with a mask layer. The appearance of the device was improved.

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

Patent Document 3 only describes that the mask layer may be formed of a black resin or other opaque coating material, but various color tones (between the mask layer and the front plate as required). Black, white, pastel color, metallic, etc.) can be provided, and in recent years, in particular, it is required to increase the brightness and whiteness of the white decorative layer.
As a method of providing this decoration layer, conventionally, a method using liquid resist coating, screen printing, or the like has been the mainstream.

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 typified by Corning's gorilla glass on the front plate (the surface directly touched by a finger). , Has been announced.
When the present inventors examined, when trying to form a white decorating layer on this tempered glass substrate using a liquid resist for forming a decorative layer or a screen printing ink, a liquid resist or a screen printing ink having a low hiding power is used. In order to form a white decorative layer, it is necessary to perform liquid resist coating and screen printing in several steps, resulting in bubbles and unevenness, a decrease in yield due to the large number of processes, etc. It has been found that there is a problem that cost reduction is not easy. Furthermore, after applying a decorative layer on tempered glass, when heated in a process for producing a circuit such as a transparent conductive layer, there is a problem that the whiteness decreases.

  On the other hand, as a white film having high heat resistance, at least (A) a thermosetting resin substantially free of silicon in the molecule and (B) a white thermosetting resin composition containing a white colorant. A multilayer film is proposed in which a layer to be formed 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 that the whiteness is lowered when heated at a high temperature in a process for producing a circuit such as a transparent conductive layer.

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

As described above, when the present inventors examined, when a white decorative layer was formed by the method described in these documents, all the characteristics of brightness, whiteness, reticulation and adhesion after transfer were satisfied. It turned out that the thing of the performance to do cannot be obtained. Moreover, it turned out that it is difficult to obtain the white decorating layer which satisfies the said characteristic with high yield.
The problem to be solved by the present invention is to provide a heat-resistant decorative coloring composition capable of obtaining a white decorative layer having good brightness, whiteness, reticulation and adhesion with a high yield. It is in.
At the same time, an electrostatic capacitance-type input device capable of thin layer / weight reduction using a heat-resistant decorative coloring composition that satisfies the above characteristics can be manufactured in a simple process with high quality. It is an object of the present invention to provide a method of manufacturing a capacitive input device, a capacitive input device obtained by the manufacturing method, and an image display device using the capacitive input device.

  On the other hand, as a result of further studies on the whiteness of the white decorative layer by the present inventors, after forming the white decorative layer, heating at a high temperature is performed when forming a transparent electrode pattern made of ITO or the like. At this time, it was found that the whiteness of the white decorative layer was significantly reduced. Therefore, by using a silicone-based resin for the coloring composition for heat-resistant decoration, it has been found that a white decorative layer having good brightness, whiteness, reticulation and adhesion can be obtained with high yield, The present invention has been reached.

（一般式（１）中、Ｒ¹は独立して、水素原子、ハロゲン原子、炭素数１〜２０の直鎖状、分岐状もしくは環状のアルコキシ基、炭素数１〜２０の直鎖状、分岐状もしくは環状のアルキル基、炭素数１〜２０の直鎖状、分岐状もしくは環状の置換アルキル基、炭素数２〜２０の直鎖状、分岐状もしくは環状のアルケニル基、炭素数６〜２０のアリール基または炭素数７〜２０のアラルキル基を表す。）
［４］ ［３］に記載の耐熱性加飾用着色組成物は、前記一般式（１）中、Ｒ¹は独立して、水素原子、炭素数１〜２０の直鎖状、分岐状もしくは環状のアルキル基、炭素数１〜６の直鎖状、分岐状もしくは環状の置換アルキル基または炭素数６〜９のアリール基を表すことが好ましい。
［５］ ［３］に記載の耐熱性加飾用着色組成物は、前記一般式（１）中、Ｒ¹は独立して、水素原子、メチル基またはトリル基を表すことが好ましい。
［６］ ［１］〜［５］のいずれか一項に記載の耐熱性加飾用着色組成物は、前記耐熱性加飾用着色組成物の全固形分に対する前記白色無機顔料の含有率が２０〜７５質量％であることが好ましい。
［７］ ［１］〜［６］のいずれか一項に記載の耐熱性加飾用着色組成物は、前記白色無機顔料が、無機物で表面処理されたルチル型酸化チタンであることが好ましい。
［８］ ［７］に記載の耐熱性加飾用着色組成物は、前記ルチル型酸化チタンが、少なくともアルミナ、ジルコニアのいずれかで表面処理されたルチル型酸化チタンであることが好ましい。
［９］ ［１］〜［８］のいずれか一項に記載の耐熱性加飾用着色組成物は、前記耐熱性加飾用着色組成物が、静電容量型入力装置前面板加飾用であることが好ましい。
［１０］ 前面板と、前記前面板の非接触側に少なくとも下記（１）および（３）〜（５）の要素を有する静電容量型入力装置の製造方法であって、［１］〜［９］のいずれか一項に記載の耐熱性加飾用着色組成物を前記前面板の非接触側に適用して少なくとも前記（１）加飾層を形成する工程を含むことを特徴とする静電容量型入力装置の製造方法。
（１）加飾層
（３）複数のパッド部分が接続部分を介して第一の方向に延在して形成された複数の第一の透明電極パターン
（４）前記第一の透明電極パターンと電気的に絶縁され、前記第一の方向に交差する方向に延在して形成された複数のパッド部分からなる複数の第二の電極パターン
（５）前記第一の透明電極パターンと前記第二の電極パターンとを電気的に絶縁する絶縁層
［１１］ ［１０］に記載の静電容量型入力装置の製造方法は、前記静電容量型入力装置がさらに、（６）前記第一の透明電極パターンおよび前記第二の電極パターンの少なくとも一方に電気的に接続され、前記第一の透明電極パターンおよび前記第二の電極パターンとは別の導電性要素を有することが好ましい。
［１２］ ［１０］または［１１］に記載の静電容量型入力装置の製造方法は、前記第二の電極パターンが透明電極パターンであることが好ましい。
［１３］ ［１０］〜［１２］のいずれか一項に記載の静電容量型入力装置の製造方法は、前記加飾層の厚みが１〜４０μｍであることが好ましい。
［１４］ ［１０］〜［１３］のいずれか一項に記載の静電容量型入力装置の製造方法は、前記（１）加飾層を、前記耐熱性加飾用着色組成物を前記前面板の非接触側に適用した後に、０．０８〜１．２ａｔｍの環境下で１８０〜３００℃に加熱して形成することが好ましい。
［１５］ ［１４］に記載の静電容量型入力装置の製造方法は、前記加飾層の加熱を、空気環境下で行うことが好ましい。
［１６］ ［１０］〜［１５］のいずれか一項に記載の静電容量型入力装置の製造方法は、前記前面板の非接触側に前記耐熱性加飾用着色組成物を適用する工程が、前記耐熱性加飾用着色組成物を印刷する工程であることが好ましい。
［１７］ ［１０］〜［１６］のいずれか一項に記載の静電容量型入力装置の製造方法は、前記（１）加飾層の前記前面板とは逆側の面上に、さらに（２）マスク層を設置することが好ましい。
［１８］ ［１７］に記載の静電容量型入力装置の製造方法は、前記第一の透明電極パターンおよび前記第二の電極パターンの少なくとも一方を、前記前面板の非接触面および前記マスク層の前記前面板とは逆側の面の両方の領域にまたがって設置することが好ましい。
［１９］ ［１７］または［１８］に記載の静電容量型入力装置の製造方法は、前記静電容量型入力装置がさらに、（６）前記第一の透明電極パターンおよび前記第二の電極パターンの少なくとも一方に電気的に接続され、前記第一の透明電極パターンおよび前記第二の電極パターンとは別の導電性要素を有し、前記（６）別の導電性要素を、少なくとも前記マスク層の前面板とは逆側の面側に設置することが好ましい。
［２０］ ［１０］〜［１９］のいずれか一項に記載の静電容量型入力装置の製造方法は、さらに、前記（１）および（３）〜（５）の要素の全てまたは一部を覆うように透明保護層を設置することが好ましい。
［２１］ ［２０］に記載の静電容量型入力装置の製造方法は、前記透明保護層を、硬化性樹脂組成物を用いて形成することが好ましい。
［２２］ ［１０］〜［２１］のいずれか１項に記載の静電容量型入力装置の製造方法は、前記静電容量型入力装置がさらに、（６）前記第一の透明電極パターンおよび前記第二の電極パターンの少なくとも一方に電気的に接続され、前記第一の透明電極パターンおよび前記第二の電極パターンとは別の導電性要素を有し、前記第二の電極パターンが透明電極パターンであり、前記（３）第一の透明電極パターン、前記（４）第二の透明電極パターンおよび前記（６）導電性要素を、硬化性樹脂組成物によって形成されたエッチングパターンを用いて透明導電材料をエッチング処理することによって形成することが好ましい。
［２３］ ［１０］〜［２１］のいずれか１項に記載の静電容量型入力装置の製造方法は、前記静電容量型入力装置がさらに、（６）前記第一の透明電極パターンおよび前記第二の電極パターンの少なくとも一方に電気的に接続され、前記第一の透明電極パターンおよび前記第二の電極パターンとは別の導電性要素を有し、前記第二の電極パターンが透明電極パターンであり、前記（３）第一の透明電極パターン、前記（４）第二の透明電極パターンおよび前記（６）導電性要素の少なくとも一つを、導電性硬化性樹脂組成物を用いて形成することが好ましい。
［２４］ ［１０］〜［２３］のいずれか１項に記載の静電容量型入力装置の製造方法は、前記前面板の非接触面に表面処理を行い、前記表面処理を施した前記前面板の非接触面上に硬化性樹脂組成物を設置することが好ましい。
［２５］ ［２４］に記載の静電容量型入力装置の製造方法は、前記前面板の表面処理に、シラン化合物を用いることが好ましい。
［２６］ ［１０］〜［２５］のいずれか１項に記載の静電容量型入力装置の製造方法は、前記前面板が、少なくとも一部に開口部を有することが好ましい。
［２７］ ［１０］〜［２６］のいずれか１項に記載の静電容量型入力装置の製造方法で製造されたことを特徴とする静電容量型入力装置。
［２８］ ［２７］に記載の静電容量型入力装置を構成要素として備えたことを特徴とする画像表示装置。 The present invention, which is a specific means for solving the above problems, is as follows.
[1] A heat-resistant decorative coloring composition comprising at least (A) a white inorganic pigment and (B) a silicone-based resin.
[2] It is preferable that the coloring composition for heat resistant decoration according to [1] further includes (C) an antioxidant.
[3] In the coloring composition for heat resistant decoration according to [1] or [2], the silicone resin is a modified silicone resin or a siloxane represented by at least the following general formula (1) in the molecule. It is preferred to include a straight silicone resin containing structure.
General formula (1)

(In the general formula (1), R ¹ is independently 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, a C 6 to 20 carbon atom Represents an aryl group or an aralkyl group having 7 to 20 carbon atoms.)
[4] The coloring composition for heat-resistant decoration according to [3], in the general formula (1), R ¹ is independently a hydrogen atom, a straight chain having 1 to 20 carbon atoms, branched or It preferably represents a cyclic 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 colored composition for heat resistant decoration according to [3], in the general formula (1), R ¹ preferably independently represents a hydrogen atom, a methyl group, or a tolyl group.
[6] The heat-resistant decorative coloring composition according to any one of [1] to [5] has a content ratio of the white inorganic pigment with respect to a total solid content of the heat-resistant decorative coloring composition. It is preferable that it is 20-75 mass%.
[7] The coloring composition for heat resistant decoration according to any one of [1] to [6] is preferably a rutile type titanium oxide in which the white inorganic pigment is surface-treated with an inorganic substance.
[8] In the coloring composition for heat resistant decoration according to [7], the rutile type titanium oxide is preferably rutile type titanium oxide surface-treated with at least one of alumina and zirconia.
[9] The coloring composition for heat resistant decoration according to any one of [1] to [8], wherein the coloring composition for heat resistant decoration is used for decorating a capacitance type input device front panel. It is preferable that
[10] A method of manufacturing a capacitive input device having a front plate and at least the following elements (1) and (3) to (5) on the non-contact side of the front plate, 9] including the step of applying at least the (1) decoration layer by applying the heat-resistant coloring composition for decoration to a non-contact side of the front plate. A method for 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 via connecting portions (4) The first transparent electrode pattern and A plurality of second electrode patterns comprising a plurality of pad portions that are electrically insulated and extend in a direction intersecting the first direction. (5) The first transparent electrode pattern and the second electrode pattern. The capacitive input device manufacturing method according to [11] [10], wherein the capacitive input device further includes (6) the first transparent layer. It is preferable to have a conductive element that is electrically connected to at least one of the electrode pattern and the second electrode pattern and is different from the first transparent electrode pattern and the second electrode pattern.
[12] In the method for manufacturing a capacitive input device according to [10] or [11], it is preferable that the second electrode pattern is a transparent electrode pattern.
[13] In the method for manufacturing a capacitive input device according to any one of [10] to [12], the thickness of the decorative layer is preferably 1 to 40 μm.
[14] The method for manufacturing a capacitance-type input device according to any one of [10] to [13] includes: (1) the decorative layer, and the heat-resistant decorative coloring composition in the front. After applying to the non-contact side of the face plate, it is preferably formed by heating to 180 to 300 ° C. in an environment of 0.08 to 1.2 atm.
[15] In the method for manufacturing a capacitive input device according to [14], it is preferable to heat the decorative layer in an air environment.
[16] The method for manufacturing the capacitance-type input device according to any one of [10] to [15], wherein the heat-resistant decorative coloring composition is applied to the non-contact side of the front plate. However, it is preferable that it is a process of printing the coloring composition for heat-resistant decoration.
[17] The method for manufacturing a capacitance-type input device according to any one of [10] to [16] is further characterized in that (1) the decorative layer has a surface on the side opposite to the front plate. (2) It is preferable to install a mask layer.
[18] In the method for manufacturing a capacitive input device according to [17], at least one of the first transparent electrode pattern and the second electrode pattern is formed by using a non-contact surface of the front plate and the mask layer. It is preferable to install across both areas of the surface opposite to the front plate.
[19] In the method for manufacturing a capacitive input device according to [17] or [18], the capacitive input device may further include (6) the first transparent electrode pattern and the second electrode. A conductive element that is electrically connected to at least one of the patterns and is different from the first transparent electrode pattern and the second electrode pattern; and (6) the another conductive element is at least the mask It is preferable to install the layer on the side opposite to the front plate.
[20] The method for manufacturing a capacitance-type input device according to any one of [10] to [19] further includes all or part of the elements (1) and (3) to (5). It is preferable to install a transparent protective layer so as to cover.
[21] In the method for manufacturing a capacitive input device according to [20], the transparent protective layer is preferably formed using a curable resin composition.
[22] In the method for manufacturing a capacitive input device according to any one of [10] to [21], the capacitive input device further includes (6) the first transparent electrode pattern and The second electrode pattern is electrically connected to at least one of the second electrode patterns, has a conductive element different from the first transparent electrode pattern and the second electrode pattern, and the second electrode pattern is a transparent electrode The pattern is (3) the first transparent electrode pattern, (4) the second transparent electrode pattern, and (6) the conductive element is transparent using an etching pattern formed of a curable resin composition. It is preferable to form the conductive material by etching.
[23] In the method for manufacturing a capacitive input device according to any one of [10] to [21], the capacitive input device further includes (6) the first transparent electrode pattern and The second electrode pattern is electrically connected to at least one of the second electrode patterns, has a conductive element different from the first transparent electrode pattern and the second electrode pattern, and the second electrode pattern is a transparent electrode A pattern, and at least one of (3) the first transparent electrode pattern, (4) the second transparent electrode pattern, and (6) the conductive element is formed using a conductive curable resin composition. It is preferable to do.
[24] The method for manufacturing a capacitive input device according to any one of [10] to [23], wherein the non-contact surface of the front plate is subjected to a surface treatment, and the surface treatment is performed before the surface treatment. It is preferable to install the curable resin composition on the non-contact surface of the face plate.
[25] In the method for 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 for 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 partially.
[27] A capacitance type input device manufactured by the method for manufacturing a capacitance type input device according to any one of [10] to [26].
[28] An image display device comprising the capacitive input device according to [27] as a constituent element.

ADVANTAGE OF THE INVENTION According to this invention, the coloring composition for heat resistant decorating which can obtain the white decorating layer with favorable brightness, whiteness, reticulation, and adhesiveness with a high yield can be provided.
According to the present invention, it is possible to manufacture a capacitive input device capable of thin layer / weight reduction using a heat-resistant decorative coloring composition that satisfies the above-mentioned characteristics in a simple process with high quality. Provided is a method for manufacturing a capacitance-type input device that can be used, a capacitance-type input device obtained by the method, and an image display device using the capacitance-type input device. can do.

It is sectional drawing which shows the structure of the electrostatic capacitance type input device of this invention. It is explanatory drawing which shows an example of the front plate in this 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 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 a schematic diagram of a dirt prevention board. It is the schematic of a dirt prevention stopper.

Hereinafter, the coloring composition for heat-resistant decoration of the present invention, the method for producing a capacitive input device, the capacitive input device, and the image display device will be described.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

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

-(A) White inorganic pigment-
As the white inorganic pigment (A), the white pigment described in paragraph [0019] of JP2009-191118A or paragraph [0109] of JP2000-175718A can be used.
Specifically, in the present invention, the white inorganic pigment includes titanium oxide (rutile type), titanium oxide (anatase type), zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate. 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, 100AQ, 100SA, 100SAK, 100SAS, 100TV, 100Z, 100ZR, 150W, 500B, 500H, 500SA, 500SAK, 500SAS, 500T, SMT-100SAM, 100SAS, 500SAM, 500SAS Manufactured), 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, 7 2, R-550, 580, 630, 670, 680, 780, 780-2, 820, 830, 850, 855, 930, 980, S-305, UT771, 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 (Ishihara Sangyo Co., Ltd.), KA-10, 15, 20, 30, KR-310, 380, KV-200, STT-30EHJ, 65C-S, 455, 485SA15, 495M, 495MC ( Titanium Industry Co., Ltd.), TA-100, 200, 300, 400, 500, TR-600, 700, 750, 840, 900 (Fuji Titanium Industry Co., Ltd.) and the like. It may be.

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

The content of the white inorganic pigment with respect to the total solid content of the coloring composition for heat-resistant decoration is 20 to 75% by mass, which is good brightness and whiteness, and simultaneously satisfies other required characteristics. It is preferable from a viewpoint of forming a decoration layer. In addition, when the coloring composition for heat-resistant decoration of the present invention is used in the method for producing a capacitance-type input device of the present invention described later, from the viewpoint of sufficiently shortening the development time, the entire decoration layer is solid. It is preferable that the content rate of the said white inorganic pigment with respect to a minute is 20-75 mass%.
As for the content rate of the said white inorganic pigment with respect to the total solid of the said coloring composition for heat resistant decorations, it is more preferable that it is 25-60 mass%, and it is still more preferable that it is 30-50 mass%.
The total solid content as used in this specification means the total mass of the non-volatile component remove | excluding the solvent etc. from the said coloring composition for heat resistant decorations.

  The white inorganic pigment (which is the same for other colorants used in the mask layer described later) is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the white inorganic pigment and the pigment dispersant in an organic solvent (or vehicle) described later. The vehicle is a portion of a medium in which a pigment is dispersed when the paint is in a liquid state, and is a liquid component that binds to the pigment to form a coating film (binder) and dissolves and dilutes it. Component (organic solvent).

  The dispersing machine used for dispersing the white inorganic pigment is not particularly limited, and is described in, for example, Asakura Kunizo, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, item 438. Known dispersing machines such as a kneader, a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described on page 310 of the document.

From the viewpoint of dispersion stability and hiding power, the white inorganic pigment as the white inorganic pigment (decorative layer-forming colorant) used in the present invention has an average primary particle size of 0.16 μm to 0.3 μm. More preferably, the thing of 0.18 micrometer-0.27 micrometer is preferable. Furthermore, the thing of 0.19 micrometer -0.25 micrometer is especially preferable. When the average particle size of the primary particles is 0.16 μm, the hiding power is suddenly lowered, and the base of the mask layer may be easily seen or the viscosity may be increased. On the other hand, when the thickness exceeds 0.3 μm, the whiteness decreases, and at the same time, the hiding power rapidly decreases, and the surface condition when applied is deteriorated.
The “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 the “number average particle size” refers to the above-mentioned particle size for many particles. The diameter is obtained and the average value of the 100 pieces is referred to.
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 Co., Ltd.) can be used.

-(B) Silicone resin-
A well-known thing can be used as said silicone resin.
Silicone-based resins are partially modified with the following silane compounds, dehydrated and condensed with modified silicone resins with various properties and silane compounds having alkoxy groups or silanol groups, utilizing the inherent properties of silicone. Can be classified as straight silicone. In the transfer film of the present invention, the silicone resin preferably 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.
Examples of the modified silicone resin include an acrylic resin-modified silicone resin (KR9706 manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by polymerizing or copolymerizing a monomer obtained by reacting an acrylic monomer such as acrylic acid with a silane compound, and a hydroxyl group of polyester. Polyester resin-modified silicone resin obtained by reacting a silane compound with an epoxy resin-modified silicone resin obtained by reacting an epoxy-containing silane compound with an amino group residue of the resin, and an alkyd resin similarly modified with a reactive silane compound. A modified silicone resin, a rubber silicone resin that directly forms a covalent bond with a resin using an oxime initiator, and the like can be used.

As straight silicone, what contains the siloxane structure represented by the following general formula (1) in a molecule | numerator at least can be used.
General formula (1)

In general formula (1), R ¹ is independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear or branched structure 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 Group or an aralkyl group having 7 to 20 carbon atoms, and R ¹ may be the same or different. That is, the straight silecone having the siloxane structure represented by the general formula (1) may be a condensate having the same siloxane structure or a co-condensation product having a different combination.

Examples of the halogen atom represented by R ¹ include a fluorine atom and a 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. Group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, cyclopentyloxy group, cyclohexyloxy group and the like.
Examples of the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. Group, 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 groups 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.
Examples of the linear, branched, or cyclic substituted alkyl group having 1 to 20 carbon atoms represented by R ¹ include an arylalkyl group, a fluoroalkyl group, a chloroalkyl group, a hydroxyalkyl group, and a (meth) acryloxyalkyl group. Groups and mercaptoalkyl groups. 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 ) Group, 3-phenyl-n-propyl group, 1-phenylbutyl group, 2-phenylbutyl group, 3-phenylbutyl group, 4-phenylbutyl group, 1-phenylpentyl group, 2-phenylpentyl group, 3- Phenylpentyl group, 4-phenylpentyl group, 5-phenylpentyl group, 1-phenylhexyl group, 2-phenylhexyl group, 3-phenylhexyl group, 4-phenylhexyl group, 5-phenylhexyl group, 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 Pentyl group, 4-naphthylpentyl group, 5-naphthylpentyl group, 1-naphthylhexyl group, 2-naphthyl 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; fluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, (trifluoromethyl) methyl group, pentafluoroethyl group , 3-fluoro-n-propyl group, 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) ) -N-propyl group, 2- (perfluoro-n-hexyl) ethyl group, (perfluoro-n-heptyl) methyl group, perfluoro-n-octyl group, 9- (trifluoromethyl) -n-nonyl Group, 8- (pentafluoroethyl) -n-octyl group, 7- (heptafluoro-n-propyl) -n-heptyl group, 6- (nonafluoro-n-butyl) -n-he 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; 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.
Examples of the linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms represented by R ¹ include a vinyl group, a 1-methylvinyl group, a 1-propenyl group, and an allyl group (2-propenyl group). 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 groups having 1 to 20 carbon atoms represented by R ¹ , arylalkyl groups are preferable, and cumyl groups are more preferable.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹ include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,3-xylyl group, and a 2,4-xylyl group. 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 1-naphthyl group, and the like. Among the aryl groups having 6 to 20 carbon atoms represented by R ¹ , other than an unsubstituted phenyl group, that is, an o-tolyl group, an m-tolyl group, a p-tolyl group, 2, 3 from the viewpoint of hardly generating benzene upon heating. -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 are preferable, o-tolyl group M-tolyl group and p-tolyl group are more preferable.
Examples of the aralkyl group having 7 to 20 carbon atoms represented by R ¹ include a benzyl group and a phenethyl group.

In the general formula (1), R ¹ is independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic group having 1 to 6 carbon atoms. A substituted alkyl group or an aryl group having 6 to 9 carbon atoms (preferably an aryl group other than an unsubstituted phenyl group from the viewpoint of being less likely to generate benzene during heating). More preferably, it represents a group or a tolyl group.
The siloxane structure represented by the general formula (1) preferably contains a methyl group as R ¹ from the viewpoint of particularly enhancing the L value of the decorative layer.

The straight silicone is also preferably a copolymer having a siloxane structure represented by two or more types of the general formula (1) in which R ¹ are different from each other. In this case, the siloxane structure represented by the general formula (1) in which R ¹ is an alkyl group and the siloxane structure represented by the general formula (1) in which R ¹ is a hydrogen atom, a substituted alkyl group, or an aryl group. And a copolymer thereof. 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 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%.

一般式（２）中、Ｒ²は上記一般式（１）のＲ¹と同様のものが使用できる同義であり、好ましい範囲もＲ¹と同様である。 The straight silicone used in the transfer film of the present invention comprises co-condensation with the siloxane structure represented by the following general formula (2) in addition to the siloxane structure represented by the general formula (1) in the molecule. Those containing a siloxane structure can also be preferably used.
General formula (2)

In general formula (2), R ² has the same meaning as that used for R ^{1 in} general formula (1), and the preferred range is also the same as R ¹ .

Specific examples of straight silicones include alkyl straight silicones (methyl straight silicones, etc.) prepared from condensation of silane compounds having an alkyl group having 1 to 20 carbon atoms and an alkoxy group, and alkyl aryls such as methyl and phenyl. Straight silicone, aryl straight silicone such as phenyl, and hydrogen straight silicone such as methyl hydrogen can be used.
More preferred are methyl-based straight silicone resins, methyl-tolyl-based straight silicone resins, methylphenyl-based straight silicone resins, and acrylic resin-modified silicone resins, which do not generate benzene during heating and are particularly preferred from the viewpoint of suppressing the decrease in brightness. Are methyl-based straight silicone resins, methyl-tolyl-based straight silicone resins, methyl-hydrogen-based straight silicone resins, and hydrogen-tolyl-based straight silicone resins.
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 transfer film of the present invention or the decorative layer described below obtained by transferring the colored layer of the transfer film of the present invention preferably has a low content of benzene as a decomposition product during heating, and does not contain benzene. Is more preferable. The content of benzene as a decomposition product during heating of the decorative layer is preferably 29 mg or less per 100 cm ^{2 of the} decorative layer, more preferably 19 mg or less, and particularly preferably 9.2 mg or less. Preferably, it is more preferably 0.01 mg or less.

  The weight average molecular weight of the straight silicone is preferably 1000 to 1000000, more preferably 2000 to 800000, and particularly preferably 2500 to 500000.

As a silane compound used to prepare a modified silicone resin and a straight silicone resin,
Tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltributoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane , Cumyltrimethoxysilane, tolyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropi 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-glycid Xylethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypro Pyrtriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxy Propyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycid Xylbutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycid Xibutyltrimethoxy , Δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltri 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) propyltri Trialkoxy such as toxisilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, triacyloxy or triphenoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropyl Methyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethyldimethoxysilane, γ-mercaptopropyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, vinylmethyl Dimethoxysilane, vinylmethyldiethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethyldiethoxysilane, α-glycidoxyethylme 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 xylpropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, dimethoxymethylsilane, trimethoxysilane, dimethylethoxysilane, diacetoxymethylsilane, diethoxymethylsilane, diethylmethyl Silane, triethylsilane, butyldimethylsilane, dimethylphenylsilane, methylphenylvinylsilane, diphenylmethylsilane, tripropylsilane, tripentyloxysilane, 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 ,as well as Poly (methylsilylene) methylene, tetrachlorosilane, trichlorosilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, fluorotrichlorosilane, fluoro Trimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, methyltrichlorosilane, methyltri-n-propoxy Silane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, 2- (trifluoromethyl) ethyltrichlorosilane, 2- (trifluoromethyl) Tiltrimethoxysilane, 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) Tiltly-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyltri 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, hydroxyethyltri Methoxysilane, hydroxy 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-mercaptopropylto Ethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n-butoxysilane, 3-mercaptopropyltri-sec-butoxysilane, vinyltrichlorosilane 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- -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] dimethoxysilane, (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) (.gamma.-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 ) (Vinyl) diethoxysilane, (methyl) (vinyl) di-n-propoxysilane, (methyl) (vinyl) di-i-propoxysilane, (methyl) (vinyl) di-n-butoxysilane, (methyl) (Vinyl) di-sec-butoxysilane, divinyldichlorosilane, divinyldimethoxysilane, Vinyldiethoxysilane, 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, chlorotrimethylsilane, bromotrimethylsilane, iodo Trimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, i-propoxytrimethylsilane, n-butoxytrime Silane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (Methoxy) (methyl) diphenylsilane, (ethoxy) (methyl) diphenylsilane and the like can be exemplified. However, the present invention is not limited to these specific examples.

As the silicone resin such as a modified silicone resin and a straight silicone resin, commercially available products can be used. For example, KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5844, X-21-5844, X-21-5845, X -21-5848, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X-22 -176B, 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-40-9 323, X-40-2460M, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR400, KR251, KR255, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706, KR165 (and above, Shin-Etsu Chemical Co., Ltd.);
SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, Toray Dow Corning);
FZ3711, FZ3722 (above, Nippon Unicar Company);
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 (Mitsubishi Chemical Corporation);
Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (above, Colcoat);
Examples include partial condensates such as glass resin GR100, GR650, GR908, GR950 (above, Showa Denko). However, the present invention is not limited to these specific examples.
Here, in the coloring composition for heat-resistant decoration of the present invention, the colored layer does not necessarily require photocuring by a combination of a photocurable resin and a photopolymerization initiator, and the colored layer is a photocurable resin. Or a photopolymerization initiator may or may not be included. Among them, when the colored layer contains an antioxidant to be described later, it does not contain a photopolymerization initiator, the function of the antioxidant is not inhibited by radicals generated when exposed to the photopolymerization initiator, From the viewpoint of sufficiently increasing the whiteness after baking. Therefore, the (B) silicone resin is preferably thermosetting.

-(C) Antioxidant-
The coloring composition for heat resistant decoration of the present invention contains an antioxidant, and the coloring composition for heat resistant decoration of the present invention is applied to the non-contact side of the front plate of the capacitance type input device described later. After the film is formed and baked, the decorative layer obtained is preferable from the viewpoint of increasing the whiteness after baking. Here, when forming a transparent electrode pattern such as ITO on the capacitance type input device, it is necessary to bake at a high temperature, but adding an antioxidant can increase the whiteness after baking. it can.
A well-known thing can be used as said antioxidant. For example, a hindered phenol type, semi-hindered phenol type, phosphoric acid type, or a hybrid type antioxidant having phosphoric acid / hindered phenol in the molecule can be used.
Preferred are phosphoric acid-based, phosphoric acid-based and hindered phenol-based or semi-hindered phenol-based, or a hybrid type antioxidant having phosphoric acid / hindered phenol in the molecule.
A commercially available antioxidant can also be used as the antioxidant. For example, IRGAFOS168 and IRGAFOS38 (both manufactured by BASF Japan) can be mentioned as phosphoric acid-based antioxidants, and IRGAMOD295 (manufactured by BASF Japan) can be listed as phosphoric acid / hindered phenol-based antioxidants. Examples of the hybrid type antioxidant having phosphoric acid / hindered phenol in the molecule include Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.).
The antioxidant is more preferably a phosphoric acid antioxidant from the viewpoint of preventing a decrease in whiteness, and IRGAFOS 168 is particularly preferable.
Although there is no restriction | limiting in particular as addition amount of the said antioxidant with respect to the said with respect to the total solid of the said coloring composition for heat resistant decorations, It is preferable that it is 0.001-10 mass%, 0.01-1 It is more preferable that it is mass%, and it is especially preferable that it is 0.05-0.2 mass%.

-Solvent-
Moreover, as a solvent at the time of manufacturing the coloring composition for heat resistant decorations of this invention, the solvent as described in Paragraph [0043]-[0044] of Unexamined-Japanese-Patent No. 2011-95716 can be used.

-Catalyst-
From the viewpoint of improving the brittleness of the decorative layer obtained by curing the colored composition for heat resistant decoration containing the silicone resin, the colored composition for heat resistant decorative composition of the present invention contains a catalyst. preferable. In particular, when two or more kinds of silicone resins are used, they are preferably used for promoting crosslinking by dehydration and dealcohol condensation reaction.
Known catalysts can be used as the catalyst.
As a preferable catalyst, tin (Sn), zinc (Zn), iron (Fe), titanium (Ti), zirconium (Zr), bismuth (Bi), hafnium (Hf), yttrium (Y), aluminum (as a metal component) Examples thereof include organic metal 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 from the viewpoint of high reaction activity, Zn or Ti is more preferable from the viewpoint of preventing cracking during baking, and Zn is particularly preferable from the viewpoint of improving pot life.
Examples of the organometallic compound catalyst containing zinc (Zn) include zinc triacetylacetonate, zinc stearate, bis (acetylacetonato) zinc (II) (monohydrate) and the like.
Examples of organometallic compound catalysts containing tin (Sn), titanium (Ti), zirconium (Zr), hafnium (Hf), and gallium (Ga) include, for example, the catalysts described in JP 2012-238636 A. It can be preferably used.
A commercially available catalyst can also be used as the catalyst. Examples thereof include zinc-based condensation catalyst D-15 (manufactured by Shin-Etsu Chemical Co., Ltd.).
In this invention, the said catalyst may be used individually by 1 type, and may use 2 or more types by arbitrary combinations and a ratio. Moreover, you may use together with a reaction accelerator and 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 during baking and improving pot life, and more preferably 0.03 to 5.0. % By mass.

-Additives-
Furthermore, you may use another additive for the said coloring composition for heat resistant decorations. Examples of the additive include surfactants described in paragraph [0017] of Japanese Patent No. 4502784, paragraphs [0060] to [0071] of JP-A-2009-237362, and paragraph [ And the other additives described in paragraphs [0058] to [0071] of JP-A No. 2000-310706.

  As mentioned above, although the centering on the case where the coloring composition for heat resistant decoration in the present invention is a non-photosensitive material, the coloring composition for heat resistant decoration is a negative type material or a positive type material as necessary. 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. From the viewpoint of enhancing the hiding power of the decorative layer.
The thickness of the colored layer is more preferably 1.5 to 38 μm, and particularly preferably 1.8 to 35 μm.

[Method for Manufacturing Capacitive Input Device]
The method for manufacturing a capacitive input device of the present invention (hereinafter also referred to as the manufacturing method of the present invention) includes at least the following (1) and (3) to (5) on the front plate and the non-contact side of the front plate. A method for producing a capacitance-type input device having the above elements, wherein the coloring composition for heat-resistant decoration of the present invention is applied to the non-contact side of the front plate to form at least the (1) decoration layer Including the step of:
(1) Decorative layer (3) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connecting portions (4) The first transparent electrode pattern and A plurality of second electrode patterns comprising a plurality of pad portions that are electrically insulated and extend in a direction intersecting the first direction. (5) The first transparent electrode pattern and the second electrode pattern. Further, the capacitive input device of the present invention may further include the following (6).
(6) A conductive element that 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 capacitive input device of the present invention, the second electrode pattern may be a transparent electrode pattern. In this specification, the second transparent electrode pattern may be described instead of the second electrode pattern, but the preferred embodiment of the second electrode pattern is the same as the preferred embodiment of the second transparent electrode pattern. is there.
Furthermore, in the method for manufacturing a capacitance-type input device according to the present invention, (2) a mask layer is further provided on the surface of the non-contact side of the front plate opposite to the front plate of the (1) decorative layer. It is preferable to do.

<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 preferred configuration of the capacitance-type input device of the present invention. 1, the capacitive input device 10 includes a front plate 1, a decorative layer 2a, a mask layer 2b, 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 are configured.

  The front plate 1 is composed of a light-transmitting substrate such as a glass substrate, and tempered glass represented by Corning gorilla glass can be used. Moreover, in FIG. 1, the side in which each element of the front layer 1 is provided is called the non-contact surface 1a. In the capacitive input device 10 of the present invention, input is performed by bringing a finger or the like into contact with the contact surface of the front plate 1 (the surface opposite to the non-contact surface 1a). Hereinafter, the front plate may be referred to as a “base material”.

Moreover, the mask layer 2b is provided on the non-contact surface of the front plate 1 through the decorative layer 2a. The mask layer 2b is a frame-like pattern around the display area formed on the non-contact side of the front panel of the touch panel, and is formed so as not to show the lead wiring or the like.
The decoration layer 2a is formed for the purpose of decoration on the mask layer 2b, that is, between the non-contact side of the touch panel front plate and the mask layer 2b.
As shown in FIG. 2, the capacitive input device 10 of the present invention includes a decorative layer 2 a and a mask layer so as to cover a part of the front plate 1 (a region other than the input surface in FIG. 2). 2b is preferably provided. Further, the front plate 1 can be provided with an opening 8 in a part of the front plate as shown in FIG. A mechanical switch by pressing can be installed in the opening 8. Since the tempered glass used as a base material has high strength and is difficult to process, it is general to form the opening 8 by forming the opening 8 before the tempering treatment and then performing the tempering treatment. . However, if the decoration layer 2a is formed on the substrate after the reinforcement treatment having the opening 8 at once using the decoration layer forming liquid resist or the screen printing ink, the resist component from the opening may be removed. In addition, there is a problem that the resist component protrudes from the glass edge in the decorative layer provided between the mask layer and the front plate that needs to form a light shielding pattern until the boundary of the front plate, and the back side of the substrate is contaminated. Although it may occur, such a problem can also be solved when forming the decoration layer 2a on the base material which has the opening part 8 by dividing the coloring composition for heat resistant decoration into several times.

On the non-contact surface of the front plate 1, a plurality of first transparent electrode patterns 3 formed by extending a plurality of pad portions in the first direction via connection portions, and a first transparent electrode pattern 3 And a plurality of second transparent electrode patterns 4 comprising a plurality of pad portions formed extending in a direction crossing the first direction, the first transparent electrode pattern 3 and the second An insulating layer 5 for electrically insulating the transparent electrode pattern 4 is formed. The first transparent electrode pattern 3, the second transparent electrode pattern 4, and the conductive element 6 to be described later are, for example, translucent conductive materials such as ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide). It can be made of a conductive metal oxide film. Examples of such metal films include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO ₂ . At this time, the film thickness of each element can be 10 to 200 nm. Further, since the amorphous ITO film is made into a polycrystalline ITO film by firing, the electrical resistance can be reduced. Moreover, said 1st transparent electrode pattern 3, the 2nd transparent electrode pattern 4, and the electroconductive element 6 mentioned later are manufactured using the electroconductive curable resin composition using the below-mentioned electroconductive fiber. You can also In addition, when forming a 1st transparent electrode pattern etc. by ITO etc., the paragraphs [0014]-[0016] etc. of patent 4506785 gazette can be referred.

  In addition, at least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4 extends over both the non-contact surface of the front plate 1 and the region of the mask layer 2 opposite to the front plate 1. Can be installed. In FIG. 1, a diagram is shown in which the second transparent electrode pattern is installed across both areas of the non-contact surface of the front plate 1 and the surface opposite to the front plate 1 of the mask layer 2. Yes. Thus, even when straddling the mask layer and the back surface of the front plate that require a certain thickness, printing and coating the heat-resistant decorative coloring composition of the present invention in several times can be simplified. In the process, it is possible to form a film continuous with the boundary of the mask portion.

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

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

  Moreover, in FIG. 1, the transparent protective layer 7 is installed 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 made of the same material or different materials. The material constituting the insulating layer 5 and the transparent protective layer 7 is preferably a material having high surface hardness and high heat resistance, and a known photosensitive siloxane resin material, acrylic resin material, or the like is used.

Hereinafter, the details of each layer will be described in the production method of the present invention.
Examples of embodiments formed in the course of the production method of the present invention include the embodiments of FIGS. FIG. 4 is a top view illustrating an example of the tempered glass 11 in which the opening 8 is formed. FIG. 5 is a top view showing an example of the front plate on which the decorative layer 2a and the mask layer 2b are formed. FIG. 6 is a top view showing an example of the front plate on which the first transparent electrode pattern 3 is formed. FIG. 7 is a top view showing an example of a front plate on which the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are formed. FIG. 8 is a top view showing an example of a front plate on which conductive elements 6 different from the first and second transparent electrode patterns are formed. These show examples embodying the above description, and the scope of the present invention is not limitedly interpreted by these drawings.

<(1) Decorative layer>
The production method of the present invention is characterized in that at least the (1) decorative layer is formed using the coloring composition for heat-resistant decoration of the present invention.

  In the capacitance type input device having the opening 8 having the configuration shown in FIG. 2, the decorative layer 2a shown in FIG. When using a photocurable resin composition or a transfer film having a photocurable resin layer, there is no resist component leakage from the opening even on a substrate (front plate) having an opening, especially to the boundary of the front plate Touch panel that has the advantage of thin layer / light weight in a simple process without contaminating the back side of the substrate because there is no protrusion of colored components from the glass edge in the decorative layer or mask layer that needs to form a light-shielding pattern Can be manufactured.

A method for forming the decorative layer using the coloring composition for heat-resistant decoration of the present invention will be described. In general, when a heat-resistant decorative coloring composition is used, it can be formed by an ordinary 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, depending on the method applied (for example, printing / coating) on the substrate. A decoration layer can be formed using the coloring composition for heat-resistant decoration of the present invention. The step of applying the heat-resistant decorative coloring composition to the non-contact side of the front plate is preferably a step of printing the heat-resistant decorative coloring composition, more preferably screen printing. .
You may combine well-known image development facilities, such as a brush and a high pressure jet, as needed. After the development, post-exposure and post-bake may be performed as necessary, and post-bake is preferably performed.

  In addition, after applying the coloring composition for heat-resistant decoration of the present invention (for example, printing / coating), in order to enhance the adhesion of the decoration layer in the drying process, the non-contact surface of the base material (front plate) in advance. Can be surface treated. As the surface treatment, it is preferable to perform a surface treatment (silane coupling treatment) using a silane compound. As the silane coupling agent, those having a functional group that interacts with the photosensitive resin are preferable. For example, a silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3 mass% aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) is sprayed for 20 seconds by a shower, and pure water shower washing is performed. To do. Thereafter, the reaction is carried out by heating. A heating tank may be used, and the reaction can be promoted by preheating the substrate of the laminator.

(Post bake process)
It is preferable to include a post-baking step after the drying step after applying (for example, printing / coating) the heat-resistant decorative coloring composition to the non-contact side of the front plate.
In the production method of the present invention, after the (1) decoration layer is applied to the non-contact side of the front plate, the heat-resistant coloring composition of the present invention is applied to the environment of 0.08 to 1.2 atm. It is preferable to heat and form at 180 to 300 ° C. from the viewpoint of achieving both whiteness and productivity.
The post-baking is more preferably performed in an environment of 0.5 atm or more. On the other hand, it is more preferable to carry out in an environment of 1.1 atm or less, and it is particularly preferred to carry out in an environment of 1.0 atm or less. Furthermore, it is more preferable to carry out in an environment of about 1 atm (atmospheric pressure) from the viewpoint of reducing the manufacturing cost without using a special decompression device. Here, conventionally, when the decorative layer (1) is formed by curing by heating, it is performed under a reduced pressure environment of a very low pressure, and the whiteness after baking is maintained by lowering the oxygen concentration. However, by using the coloring composition for heat-resistant decoration of the present invention, the whiteness of the decorative layer can be increased even after baking in the above pressure range.
The post-baking temperature 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 a nitrogen substitution environment, but it is particularly preferable to perform the post-bake from the viewpoint of reducing the manufacturing cost without using a special decompression device.

(Other processes)
The manufacturing method of this invention may have other processes, such as a post-exposure process.
When forming the said decoration layer when the said coloring composition for heat resistant decorations has a photocurable resin layer, it is preferable that a post-exposure process is included. Even if the post-exposure step is performed only from the surface direction on the side in contact with the substrate of the coloring composition for heat-resistant decoration, or only from the surface direction on the side not in contact with the transparent substrate, You may carry out from a double-sided direction.

<(2) Mask layer>
In the manufacturing method of this invention, the mask layer 2b, the 1st transparent electrode pattern 3, the 2nd transparent electrode pattern 4, the insulating layer 5, the electroconductive element 6, and the transparent protective layer 7 as needed. It is preferable to form at least one element using the curable resin layer. Transfer the curable resin layer of the transfer film to mask layer 2b, first transparent electrode pattern 3, second transparent electrode pattern 4, insulating layer 5, conductive element 6, and as required. It is also preferable to include a step of forming at least one element with the transparent protective layer 7. The “curable resin layer” refers to a layer (also referred to as a colored layer) obtained by forming the colored composition for heat-resistant decoration of the present invention, or a “photocurable property” composed of a photocurable resin composition. It means “resin layer”.
At least one element 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 a light It is more preferable to form the curable resin layer, and it is particularly preferable to use a photocurable resin composition.
For example, when forming the black mask layer 2, the surface of the said front plate 1 is used using the black coloring composition and the photocurable resin composition which has a black photocurable resin layer as the said decoration layer. The said black decoration layer can be formed.

  Further, by using a photocurable resin composition for forming the mask layer 2b that needs light shielding properties, it is possible to form a high-quality mask layer 2b that is free from light leakage due to unevenness, repelling, bubbles, and the like.

A colorant can be used when a colored layer made of a colored composition or a photocurable resin layer made of the photocurable resin composition is used as a mask layer. As the colorant used in the present invention, known colorants (organic pigments, inorganic pigments, dyes, etc.) can be suitably used. In the present invention, 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 the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, and graphite. Among these, carbon black is preferable.
For use as a mask layer of other colors, pigments or dyes described in paragraphs [0183] to [0185] of Japanese Patent No. 4546276 may be mixed and used. Specifically, the pigments and dyes described in paragraphs [0038] to [0054] of JP-A-2005-17716, and the pigments described in paragraphs [0068] to [0072] of JP-A-2004-361447. The coloring agents described in paragraph numbers [0080] to [0088] of JP-A-2005-17521 can be suitably used.
The colorant used in addition to the decorative layer used in the present invention preferably has a number average particle diameter of 0.001 μm to 0.1 μm, more preferably 0.01 μm to 0.08 μm, from the viewpoint of dispersion stability. . The “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for a large number of particles, This 100 average value is said.

  The photocurable resin layer preferably has the following configuration.

There is no restriction | limiting in particular as long as it is not contrary to the meaning of this invention as said monomer used for the said photocurable resin layer, A well-known polymeric compound can be used.
As the polymerizable compound, the polymerizable compounds described in paragraphs [0023] to [0024] of Japanese Patent No. 4098550 can be used.

The binder used in the photocurable resin layer is not particularly limited as long as it is not contrary to the gist of the present invention, and a known polymerizable compound can be used.
When the composition for forming the photocurable resin layer is a negative material, the photocurable resin layer preferably contains an alkali-soluble resin, a polymerizable compound, a polymerization initiator, or a polymerization initiation system. Further, colorants, additives, and the like are used, but are not limited thereto.
Examples of the alkali-soluble resin contained in the photocurable resin layer having the photocurable resin include paragraphs [0025] of JP2011-95716A, paragraphs [0033] to [0052] of JP2010-237589A. Can be used.
When the composition for forming the photocurable resin layer is a positive material, for example, a material described in JP-A-2005-221726 is used for the photocurable resin layer, but the material is not limited thereto. .

  As said photoinitiator used for the said photocurable resin layer, the polymeric compound as described in [0031]-[0042] of Unexamined-Japanese-Patent No. 2011-95716 can be used.

-Additives-
Furthermore, an additive may be used for the photocurable resin layer. Examples of the additive include surfactants described in paragraph [0017] of Japanese Patent No. 4502784, paragraphs [0060] to [0071] of JP-A-2009-237362, and paragraph [ And the other additives described in paragraphs [0058] to [0071] of JP-A No. 2000-310706.

-Solvent-
Moreover, as a solvent of a photocurable resin composition, the solvent as described in Paragraph [0043]-[0044] of Unexamined-Japanese-Patent No. 2011-95716 can be used.

  As described above, the case where the photocurable resin layer is a negative type material has been mainly described, but the 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 the first direction via connection portions>

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. Preferably, the transparent conductive material is formed by etching 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 transparent electrode pattern, and the conductive element. It is preferable that the conductive curable resin composition is used.
That is, the first transparent electrode pattern 3 is preferably formed using an etching process or a conductive curable resin composition.

(Etching process)
When the first transparent electrode pattern 3 is formed by the etching process, there is no particular limitation on the etching process method. For example, the first transparent electrode pattern 3 is made of, for example, ITO on the non-contact surface of the front plate 1 on which the mask layer 2b is formed. A transparent electrode layer is formed by sputtering, then formed on the transparent electrode layer using a composition having a photocurable resin for etching, an etching pattern is formed by mask exposure / development, and then the transparent electrode The method of forming the 1st transparent electrode pattern 3 grade | etc., Can be mentioned by etching a layer, patterning a transparent electrode, and removing an etching pattern.
Before forming a composition having a photocurable resin for etching on the transparent electrode layer, a front plate is inserted into the antifouling plate 13 shown in FIG. 10, and the substrate has openings 8 as shown in FIG. When it has, it is preferable to insert the antifouling plug 14 shown in FIG. It is preferable that the stain prevention plate and the stain prevention plug are made of silicone.
Also when the transfer film having the photocurable resin layer is used as an etching resist (etching pattern), a resist pattern can be obtained in the same manner as in the above method. For the etching, etching and resist stripping can be applied by a known method described in paragraphs [0048] to [0054] of JP 2010-152155 A.

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

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

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

  Examples of the stripping solution include inorganic alkali components such as sodium hydroxide and potassium hydroxide, organic alkali components such as tertiary amine and quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or these. What was melt | dissolved in this mixed solution is mentioned. You may peel by the spray method, the shower method, the paddle method etc. using the said peeling liquid.

(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 forming the curable resin layer using the application of the photocurable resin composition or the transfer of the photocurable resin on the temporary support and patterning, after forming the transparent conductive layer on the entire surface of the substrate, A desired transparent conductive layer pattern can be obtained by dissolving and removing the photocurable resin layer together with the deposited transparent conductive layer (lift-off method).

  Conductive fibers and the like are contained in the conductive curable resin layer.

-Conductive curable resin layer (conductive fiber)-
When the transfer film on 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 an electroconductive fiber, Although it can select suitably according to the objective, A solid structure or a hollow structure is preferable.
Here, the fiber having a solid structure may be referred to as “wire”, and the fiber having a hollow structure may be referred to as “tube”. In addition, a conductive fiber having an average minor axis length of 5 nm to 1,000 nm and an average major axis length of 1 μm to 100 μm may be referred to as “nanowire”.
In addition, conductive fibers having an average minor axis length of 1 nm to 1,000 nm, an average major axis length of 0.1 μm to 1,000 μm, and having a hollow structure may be referred to as “nanotubes”.
The material of the conductive fiber is not particularly limited as long as it has conductivity, and can be appropriately selected according to the purpose. However, at least one of metal and carbon is preferable, and among these, The conductive fiber is particularly preferably at least one of metal nanowires, metal nanotubes, and carbon nanotubes.

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

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

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

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

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

  The thickness of the conductive curable resin layer is preferably from 0.1 to 20 μm, more preferably from 0.5 to 18 μm, from the viewpoint of process suitability such as the stability of the coating solution and the drying time during coating and the development time during patterning. Preferably, 1-15 micrometers is especially preferable. 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 0.05 to 30% by mass from the viewpoints of conductivity and stability of the coating liquid. Is more preferable, and 0.1 to 20% by mass is particularly preferable.

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

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

<(5) Insulating layer that electrically insulates the first transparent electrode pattern and the second transparent electrode pattern>
When the insulating layer 5 is formed, the transfer film of the present invention having an insulating colored layer as the colored layer, an insulating colored composition, or an insulating photocurable resin as the photocurable resin layer. Using the transfer film or photocurable resin composition having the photocurable resin layer having a layer, the insulating colored layer or photocured on the surface of the front plate 1 on which the first transparent electrode pattern is formed. A functional resin layer can be formed.
When forming the insulating layer, 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) Conductivity that is electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern and is different from the first transparent electrode pattern and the second transparent electrode pattern Element>
Said another electroconductive element 6 can be formed using the said etching process or the transfer film or electroconductive curable resin composition which has the said electroconductive curable resin layer.

<(7) Transparent protective layer>
When the transparent protective layer 7 is formed, 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. Can be formed by transferring the transparent colored layer or the transparent photocurable resin layer to the surface of the front plate 1 on which is formed.
When forming a transparent protective layer using a transfer film, the 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 protection ability. Particularly preferred is ˜3 μm.

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

Hereinafter, the present invention will be described more specifically with reference to examples.
The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below. Unless otherwise specified, “%” and “parts” are based on mass.

[Synthesis Example 1]
<Synthesis of tolyltrimethoxysilane ((4-methylphenyl) trimethoxysilane)>
Magnesium 19.0 g (0.784 mol) and tetrahydrofuran 300 mL were added to a 500 mL four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, and iodine pieces were added. A small amount of tolyl chloride was added dropwise to start the reaction, and then 94.4 g (0.746 mol) of tolyl chloride was added dropwise at 5 to 10 ° C. to prepare a Grignard reagent.

  Next, 568 g (3.73 mol) of normal methyl silicate was charged into a 1000 mL four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, and the Grignard reagent prepared above at a temperature of 60 to 70 ° C. It was added dropwise over time. Thereafter, the mixture was cooled and the precipitated magnesium salt was filtered, and then the solvent was distilled off, followed by rectification and recovery. As a result of GC analysis of the obtained fraction, GC purity was 98.8%, and NMR and IR analysis revealed that it was tolyltrimethoxysilane (bp 74 to 75 ° C.).

(Synthesis of tolyltrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% condensate)
A 500 mL four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 2.1 g of 25% tetramethylammonium hydroxide aqueous solution and 7.5 g of water, and 60 mL of 2-propanol and 30 mL of toluene were added. It was. A solution of 26.6 g (0.195 mol) of methyltrimethoxysilane and 17.8 g (0.084 mol) of tolyltrimethoxysilane in 30 mL of toluene was placed in a dropping funnel and dropped at a temperature of 35 to 45 ° C. with stirring. . After completion of dropping, the mixture was aged for 2 hours, cooled to room temperature, and extracted by adding 90 mL of toluene and 90 mL of water. After putting into the separatory funnel and discharging the aqueous layer, it was washed with dilute acetic acid aqueous solution, and after discharging the aqueous layer, it was washed with water four times. Thereafter, the oil layer was filtered through a 0.5 μm PTFE filter and concentrated to prepare a toluene 50% by mass solution to obtain a toluene solution of a tolyltrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% condensate.

[Synthesis Example 2]
<Synthesis of benzyltrimethoxysilane>
In Synthesis Example 1, benzyltrimethoxysilane was prepared using equimolar amounts of benzyl chloride instead of tolyl chloride.

(Synthesis of benzyltrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% condensate)
In the synthesis method of the tolyltrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% copolymer of Synthesis Example 1, in the same manner except that equimolar amount of benzyltrimethoxysilane was used instead of tolyltrimethoxysilane, A toluene solution of a 30 mol% / 70 mol% condensate of trimethyltrimethoxysilane / methyltrimethoxysilane was obtained.

[Synthesis Example 3]
<Synthesis of cumyltrimethoxysilane>
In Synthesis Example 1, cumyltrimethoxysilane was prepared using equimolar amounts of cumyl chloride instead of tolyl chloride.

(Synthesis of cumyltrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% condensate)
In the synthesis method of the tolyltrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% condensate of Synthesis Example 1, the same procedure was applied except that equimolar amount of cumyltrimethoxysilane was used instead of tolyltrimethoxysilane. A toluene solution of rutrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% condensate was obtained.

[Synthesis Example 4]
(Synthesis of tolyltrimethoxysilane / ethyltrimethoxysilane 30 mol% / 70 mol% condensate)
In Synthesis Example 1, an equimolar amount of ethyltrimethoxysilane was used instead of methyltrimethoxysilane to obtain a toluene solution of a tolyltrimethoxysilane / ethyltrimethoxysilane 30 mol% / 70 mol% condensate.

[Synthesis Example 5]
(Synthesis of tolyltrimethoxysilane / propyltrimethoxysilane 30 mol% / 70 mol% condensate)
In Synthesis Example 1, instead of methyltrimethoxysilane, an equimolar amount of propyltrimethoxysilane (Synthesis Example 5) was used to obtain a toluene solution of a tolyltrimethoxysilane / propyltrimethoxysilane 30 mol% / 70 mol% condensate.

[Synthesis Example 6]
(Synthesis of methyltrimethoxysilane / methyldimethoxysilane 90 mol% / 10 mol% condensate)
In the synthesis method of the tolyltrimethoxysilane / methyltrimethoxysilane 30 mol% / 70 mol% copolymer of Synthesis Example 1, the total number of moles of tolyltrimethoxysilane / methyltrimethoxysilane added was kept constant while maintaining A tomethyltrimethoxysilane / methyldimethoxysilane 90 mol% / 10 mol% condensate (methyl-hydrogen type silicone resin) was added in the same manner except that the molar ratio of methoxysilane and methyldimethoxysilane was 90 mol% / 10 mol%. ) Was obtained.

[Example 1]
~ Preparation of coloring composition for heat resistant decoration of the present invention ~
The coloring composition for heat resistant decoration of the following prescription L1 was prepared and used as the coloring composition for heat resistant decoration of Example 1.
(Coloring composition for heat-resistant decoration: Formula L1)
Silicone resin KR-311 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Xylene solution of straight silicone (solid content 50% by mass): 209 parts by mass, white pigment dispersion 1 (the following composition): 123 parts by mass, antioxidant (Sumilyzer GP, manufactured by Sumitomo Chemical Co., Ltd.)
: 0.195 parts by mass / surfactant (trade name: MegaFuck F-780F, manufactured by DIC Corporation)
: 0.78 parts by mass

-Composition of white pigment dispersion 1-
・ Titanium oxide (CR97 manufactured by Ishihara Sangyo; alumina / zirconia-treated rutile type,
Primary particle diameter 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% by mass
・ Methyl ethyl ketone (manufactured by Tonen Chemical Co., Ltd.): 26.5% by mass

<Formation of decorative layer>
A glass cleaner liquid adjusted to 25 ° C. was sprayed on a tempered glass (300 mm × 400 mm × 0.7 mm) formed with an opening (15 mmΦ) for 20 seconds with a shower and washed with a rotating brush having nylon hair. After washing with water shower, a silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3 mass% aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) is sprayed for 20 seconds with a shower. Washed with pure water shower. This substrate was heated at 110 ° C. for 10 minutes with a substrate preheating device, and then allowed to cool to room temperature. On the obtained silane coupling-treated glass substrate, printing ink was applied with a screen printer (made by Mishima Corporation; UDF-5L, mesh size 250 μm) using the coloring composition for heat-resistant decoration (formulation L1). Screen printing was carried out, and it was made tack-free by drying at 100 ° C. for 10 minutes. The thickness after drying the ink was 6 μm. Further, screen printing was performed in the same manner as described above, followed by drying at 100 ° C. for 10 minutes. This printing to drying process was repeated a total of 6 times. It dried at 150 degreeC for 30 minutes, and obtained the white colored layer L1.

Then, using an oven equipped with an exhaust system, a post-baking treatment is performed in air at 240 ° C. for 60 minutes under atmospheric pressure (1 atm) to form a colored layer as a decorative layer. When the film thickness was measured, a front plate L1 on which a decorative layer having a film thickness of 36 μm was formed was obtained.
When the brightness 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 of the decoration layer of the front plate was judged visually by the following method, there was no problem. Furthermore, the amount of benzene generated when baked by the following method was 19.1 mg per 100 cm ² of the decorative layer, which was a practical level.

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

<< Evaluation of front plate with decorative layer >>
(Evaluation of brightness)
In the front plate in which the decorative layer is formed on the tempered glass, the measurement is performed using a 938 Spectrodensitometer manufactured by X-Rite, using black paper as an underlay from the surface opposite to the surface on which the decorative layer is formed. Evaluated. The practical level is D or more, preferably C or more.
<Evaluation criteria>
AA: L value 87 or more A: L value 85 or more and less than 87 B: L value 83 or more and less than 85 C: L value 81 or more and less than 83 D: L value 77 or more and less than 81 E: L value less than 77 1.

(Evaluation of whiteness)
As shown above, the decorative layer on the tempered glass was post-baked at 240 ° C. for 60 minutes in the air under atmospheric pressure (1 atm) after the transfer as described above. The whiteness was evaluated according to the evaluation criteria. The practical level is C or higher.
<Evaluation criteria>
A: Number of people recognized as yellowish 0-1 people B: Number of people recognized as yellowish 2-3 People C: Number of people recognized yellowish 4-5 people D: Number of people recognized as yellowish 6-10 people E: Number of people recognized as yellowish 11 or more The results of evaluation are shown in Table 1 below.

(Reticulation evaluation)
The front plate with the decorative layer formed on the tempered glass is allowed to stand for 24 hours in an environment at 23 ° C. and 50% relative humidity, and then the surface of the decorative layer on the front plate and the surface on which the decorative layer is formed are opposite to each other. The surface was observed with a microscope using reflected light and transmitted light, and evaluated according to the following criteria. C and above are practical levels.
<Evaluation criteria>
A: The generation of fine “wrinkles” on the surface of the decorative layer pattern is not recognized at all and is very good.
B: Although generation | occurrence | production of the very weak "wrinkle" was recognized only in the center part of the decoration layer pattern surface, it cannot recognize from the surface opposite to the surface in which the decoration layer was formed, and is favorable.
C: The occurrence of fine wrinkles on the surface of the decorative layer pattern was slightly observed, but it was not recognized from the surface opposite to the surface on which the decorative layer was formed, and it was normal at a level causing no problem in practice.
D: Occurrence of fine “wrinkles” is considerably observed, and weak unevenness is observed from the surface opposite to the surface on which the decorative layer is formed, which is a bad level.
E: Generation of fine “wrinkles” or the like was observed on the entire surface, and unevenness was observed from the surface opposite to the surface on which the decorative layer was formed.
The evaluation results are shown in Table 1 below.

(Evaluation of yield)
500 front plates each having a decorative layer formed on tempered glass were prepared, and the yield of those usable was examined.
<Evaluation criteria>
A: The yield exceeded 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 is 88% or more and less than 91%, which is normal.
D: The yield is 83% or more and less than 88%, which is bad.
E: The yield is less than 83%, which is very bad.
The evaluation results are shown in Table 1 below.

(Evaluation of decorative layer adhesion)
JIS K 5600-5-6: The decorative layer of the front plate in which the decorative layer is formed on the tempered glass according to ISO 2409 (cross-cut method) is 1 mm wide, cut, and peeled off with cellophane tape. The presence of surface peeling and pinholes was observed. C and above are practical levels.
<Evaluation criteria>
A: The decoration layer component was not peeled off at all, and the adhesion was very good.
B: Although there was a slight peeling of the decorative layer component only at the cut edge, there was no part of the mesh at a good level.
C: The peel-off of the decorative layer component is 0% to less than 2%, which is a practical level, and is normal.
D: Peeling of the decorative layer component is 2% or more and less than 5%, and peeling of the mass decorative layer component is recognized, and repair is necessary and bad for practical use.
E: 5% or more of the square decoration layer component is peeled off, and repair is necessary for practical use.
The evaluation results are shown in Table 1 below.

(Evaluation of dirt on opening)
The opening part 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 the decorative layer component was present as dirt. C and above are practical levels.
<Evaluation criteria>
A: The opening does not have any dirt of the decorative layer component, and is very good.
B: Slight dirt of the decorative layer component was observed only at the opening edge, but it was good enough to be used.
C: Dirt of the decorative layer component of about several μm was recognized from the edge of the opening to the inside of the opening, but it can be used practically and is normal.
D: Although the stain of the decorative layer component was recognized from the edge of the opening to the middle of the thickness of the glass on the inner side of the opening, repair was necessary and bad for practical use.
E: From the edge of the opening to the inside of the opening and from the back side of the glass, contamination of the decorative layer components is recognized and very bad.
The evaluation results are shown in Table 1 below.

(Evaluation of missing openings)
The periphery of the opening of the front plate on which the decorative layer was formed on the tempered glass was observed with a microscope, and the presence of peeling of the decorative layer component and pinholes was 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 only at the edge of the opening, but there was no other part, and it was a good level.
C: Although peeling of the decorative layer component of several μm around the edge of the opening was observed, it can be used practically and is normal.
D: Peeling of the decorative layer component was observed with a width of several mm around the opening, and repair was necessary and bad for practical use.
E: Peeling of the decorative layer component was observed with a width of several centimeters around the opening.
The evaluation results are shown in Table 1 below.

(Benzene generation amount)
The coloring composition for heat resistant decoration of Formula L1 was apply | coated on the tempered glass. Next, the oven was dried at 105 ° C. for 30 minutes to obtain a decorative layer. The decorative layer of a certain area is scraped from the tempered glass, the sample is put in a sample tube, heated directly at 280 ° C. for 15 minutes under He gas (including the temperature rising time from room temperature) with a heat desorption apparatus, and then GC- MS measurement was performed.
For the calibration curve, a commercially available reagent benzene was used, and after collecting in a TENAX adsorption tube by an existing method, the same heat desorption measurement as that of the sample was performed.
The GC column was DB-5MS manufactured by Agilent, and held at 40 ° C. for 3 minutes, and then temperature measurement was performed. MS detection was performed by EI ionization, and the chromatographic peak area of benzene was used for quantification.
・ Heat desorption device Company name Nippon Analytical Industries, Ltd. Device name Heat desorption device Model JTD-505III
・ GC-MS
Company name Shimadzu Corporation Device name Gas chromatograph mass spectrometer Model QP2010Ultra
<Evaluation criteria>
AA: The amount of benzene generated was very good at less than 0.01 mg / 100 cm ² .
A: The amount of generated benzene was 0.01 mg / 100 cm ² or more and less than 9.2 mg / 100 cm ² , which was good.
B: The amount of benzene generated was normal at 9.2 mg / 100 cm ² or more and less than 19 mg / 100 cm ² .
C: The amount of benzene generated is 19 mg / 100 cm ² or more and less than 29 mg / 100 cm ² , and can be used practically.
D: Poor when the amount of benzene generated is 29 mg / 100 cm ² or more.
The evaluation results are shown in Table 1 below.

<Formation of mask layer>
<Preparation of coating solution for forming mask layer>
As a mask layer forming coating solution, a coating solution having the following formulation K1 was prepared.

(Mask layer forming coating solution: Formula 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 (manufactured by Daicel Chemical Industries): 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 = 78/22 molar ratio)
Random copolymer, weight average molecular weight 38,000): 10.8 parts by mass Phenothiazine (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.01 parts by mass DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku Co., Ltd.) Made)
Propylene glycol monomethyl ether acetate solution (76% by mass)
: 5.5 parts by mass · 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bis (ethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine
: 0.4 parts by mass / surfactant (trade name: MegaFuck F-780F, manufactured by Dainippon Ink Co., Ltd.)
: 0.1 parts by mass

-Composition of K pigment dispersion 1-
Carbon black (trade name: Nipex 35, manufactured by Degussa): 13.1% by mass
・ The following dispersant 1: 0.65 mass%
Binder 1 (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, weight average molecular weight 37,000): 6.72% by 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 / methacrylic acid = 72/28 molar ratio random copolymer, 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 (hereinafter also referred to as a front plate with a decorative layer) was washed in the same manner as the cleaning of the tempered glass substrate in the formation of the decorative layer.
Printing ink was screen-printed with a screen printing machine (manufactured by Mishima Corp .; UDF-5L, mesh size 250 μm) using the mask layer-forming coating liquid formulation K1, and was tack-free by drying at 100 ° C. for 10 minutes. The thickness after drying the ink was 5 μm. Further, screen printing was performed in the same manner as described above, followed by drying at 100 ° C. for 10 minutes. (The film thickness of the photocurable resin layer for forming the mask layer was 2.2 μm). Then, with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp, the exposure mask was passed through. Without exposure, exposure was performed at an exposure amount of 1000 mJ / cm ² (i-line).
Further, a post-bake treatment at 240 ° C. for 80 minutes is performed, and a mask layer and a decorative layer having an optical density of 4.0 and a film thickness of 2.0 μm are formed in the order of the front plate, the decorative layer, and the mask layer. Got.

<Formation of first transparent electrode pattern>
<Formation of transparent electrode layer>
A front plate on which a decoration layer and a mask layer are formed is introduced into a vacuum chamber, and an ITO target (indium: tin = 95: 5 (molar ratio)) with a SnO ₂ content of 10% by mass is used for DC. An ITO thin film having a thickness of 40 nm was formed by magnetron sputtering (conditions: substrate 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 80Ω / □.

<Preparation of coating liquid E1 for photocurable resin layer for etching>
The coating liquid formulation E1 for photocurable resin layers for etching shown below was prepared.

(Coating liquid for photocurable resin layer for etching: prescription E1)
Methyl methacrylate / styrene / methacrylic acid copolymer (copolymer composition (mass%): 31/40/29, mass average molecular weight 60000,
Acid value 163 mg KOH / g): 16 parts by mass Monomer 1 (Brand name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.): 5.6 parts by mass Tetraethylene oxide monomethacrylate 0.5 mol addition of hexamethylene diisocyanate Product: 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'-tetraphenyl biimidazole: 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, manufactured by Dainippon Ink 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>
In the same manner as the formation of the mask layer, the front plate on which the decorative layer, the mask layer, and the transparent electrode layer were formed was washed and dried. 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 mmΦ) of the substrate. Next, the front plate edge and the stain prevention plate, and the opening edge and the inside of the prevention plug were prevented from being stained. In addition, adjustment was performed so that the glass and the spacer surface were flat.
The above coating liquid for etching photocurable resin layer: Formula E1 was applied using a coater for glass substrate having a slit-like nozzle (manufactured by FS Japan Co., Ltd., trade name: MH-1600). Subsequently, after part of the solvent was dried by VCD (vacuum dryer, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, the periphery of the substrate was measured by 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 thickness of 2.0 μm on the tempered glass (liquid resist method).
With a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and the exposure mask (quartz exposure mask having a frame pattern) standing vertically, the exposure mask surface The distance between the photocurable resin layers for etching was set to 200 μm, and pattern exposure was performed at an exposure amount of 200 mJ / cm ² from the photocurable resin layer for etching.
The front plate was removed from the anti-stain plate 13, and the anti-stain plug 14 made of silicone resin was removed from the opening (15mmΦ) of the substrate.
Next, a triethanolamine developer (containing 30% by mass of triethanolamine, a trade name: T-PD2 (manufactured by FUJIFILM Corporation) diluted 10 times with pure water) at 25 ° C. for 100 seconds, A surfactant-containing cleaning solution (trade name: T-SD3 (manufactured by FUJIFILM Corporation) diluted 10-fold with pure water) was treated at 33 ° C. for 20 seconds, using a rotating brush and an ultra-high pressure cleaning nozzle. The residue was removed, and a post-bake treatment at 130 ° C. for 30 minutes was further performed to obtain a front plate on which a decorative layer, a mask layer, a transparent electrode layer, and a photocurable resin layer pattern for etching were formed.

  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 tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), The transparent electrode layer which is treated for 100 seconds, dissolves and removes the exposed transparent electrode layer not covered with the photocurable resin layer for etching, and has a decorative layer, a mask layer, and a photocurable resin layer pattern for etching. A front plate with a pattern was obtained.

  Next, a front plate with a transparent electrode layer pattern with a photocurable resin layer pattern for etching was applied to a resist stripping solution (N-methyl-2-pyrrolidone, monoethanolamine, surfactant (trade name: Surfynol 465). , Manufactured by Air Products Co., Ltd.), immersed in a resist stripping tank containing a liquid temperature of 45 ° C., treated for 200 seconds, removed the photocurable resin layer for etching, decorated layer, mask layer, and non-front plate A front plate having a first transparent electrode pattern installed as shown in FIG. 1 across both the contact surface and the region of the mask layer opposite to the front plate was obtained.

<Formation of insulating layer>
<Preparation of insulating layer forming coating solution>
The following coating solution formulation W1 for forming an insulating layer was prepared.

(Insulating layer forming coating solution: Formula W1)
Binder 3 (cyclohexyl methacrylate (a) / methyl methacrylate (b) / methacrylic acid copolymer (c) glycidyl methacrylate adduct (d) (composition (% by mass): a / b / c / d = 46/1) / 10/43, mass average molecular weight: 36000, acid value 66 mgKOH / g) 1-methoxy-2-propanol, methyl ethyl ketone solution (solid content: 45%)): 12.5 parts by mass DPHA (dipentaerythritol hexaacrylate) Manufactured by Nippon Kayaku Co., Ltd.)
Propylene glycol monomethyl ether acetate solution (76% by mass)
: 1.4 parts by mass / urethane monomer (trade name: NK Oligo UA-32P, manufactured by Shin-Nakamura Chemical Co., Ltd .: non-volatile content 75%, propylene glycol monomethyl ether acetate:
25%): 0.68 parts by mass. Tripentaerythritol 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 (Brand name: Irgacure 379, manufactured by BASF): 0.17 parts by mass Dispersant (Brand name: Solsperse 20000, manufactured by Avicia): 0.19 parts by mass, interface Activator (Brand name: Megafuck F-780F, manufactured by Dainippon Ink)
: 0.05 parts by mass-Methyl ethyl ketone: 23.3 parts by mass-MMPGAc (manufactured by Daicel Chemical Co., Ltd.): 59.8 parts by mass The viscosity at 100 ° C. after removing the solvent of the coating liquid W1 for forming the insulating layer is 4000 Pa.・ It was sec.

Similarly to the formation of the photocurable resin layer for etching, a 1.4 μm thick photocurable resin layer for the insulating layer was formed on the front plate.
Subsequently, the distance between the exposure mask (quartz exposure mask having the insulating layer pattern) surface and the photocurable resin layer for etching is set to 100 μm, and pattern exposure is performed at an exposure amount of 150 mJ / cm ² (i-line). did.

  Next, a sodium carbonate / sodium hydrogen carbonate developer (trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 5 times with pure water) at 25 ° C. for 50 seconds, surfactant-containing cleaning solution (Trade name: T-SD3 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) was treated at 33 ° C. for 20 seconds, and the residue was removed with a rotating brush and an ultra-high pressure washing nozzle. Furthermore, the post-baking process for 230 degreeC and 60 minutes was performed, and the front board which formed the decoration layer, the mask layer, the 1st transparent electrode pattern, and the insulating layer pattern was obtained.

<< Formation of second transparent electrode pattern >>
<Formation of transparent electrode layer>
In the same manner as 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 (condition: substrate temperature 50 Before forming an ITO thin film having a thickness of 80 nm and an ornamental layer, a mask layer, a first transparent electrode pattern, an insulating layer pattern, and a transparent electrode layer. A face plate was obtained. The surface resistance of the ITO thin film was 110Ω / □.

Similarly to the formation of the first transparent electrode pattern, using the coating liquid formulation E1 for photocurable resin layer for etching, a decoration layer, a mask layer, a first transparent electrode pattern, an insulating layer pattern, a transparent electrode layer A front plate on which a photocurable resin layer pattern for etching was formed was obtained (post-baking treatment; 130 ° C., 30 minutes).
Furthermore, in the same manner as in the formation of the first transparent electrode pattern, the etching is performed (30 ° C., 50 seconds), and the photocurable resin layer for etching is removed (45 ° C., 200 seconds). 1 as shown in FIG. 1 across the areas of the layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the non-contact surface of the front plate and the surface of the mask layer opposite to the front plate. Thus, a front plate on which the second transparent electrode pattern was formed was obtained.

<< Formation of Conductive Element Separate from First and Second Transparent Electrode Pattern >>
In the same manner as in the formation of the first and second transparent electrode patterns, the front plate on which the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, and the second transparent electrode pattern are formed is a DC magnetron. A front plate on which an aluminum (Al) thin film having a thickness of 200 nm was formed was obtained by sputtering.

In the same manner as in the formation of the first and second transparent electrode patterns, using the coating liquid formulation E1 for the photocurable resin layer, the decorative layer, the mask layer, the first transparent electrode pattern, the 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-bake treatment; 130 ° C., 30 minutes).
Furthermore, in the same manner as in the formation of the first transparent electrode pattern, the etching is performed (30 ° C., 50 seconds), and the photocurable resin layer for etching is removed (45 ° C., 200 seconds). A front plate on which a conductive element different from the 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 was formed was obtained.

<Formation of transparent protective layer>
In the same manner as the formation of the insulating layer, the coating liquid formulation W1 for forming the insulating layer is applied and dried on the front plate formed up to the conductive element different from the first and second transparent electrode patterns, and the exposure mask is used. Without exposing the front surface at an exposure amount of 200 mJ / cm ² (i-line), developing, post-exposure (1000 mJ / cm ² ), and post-baking treatment, the decorative layer, mask layer, first transparent electrode pattern, insulation Front plate 1 in which an insulating layer (transparent protective layer) is laminated as shown in FIG. 1 so as to cover all the conductive elements different from the layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns. Got. The obtained front plate 1 was used as the capacitive input device of Example 1.

<< Production of image display device (touch panel) >>
The liquid crystal display element manufactured by the method described in Japanese Patent Application Laid-Open No. 2009-47936 is pasted with the previously manufactured front plate 1 (capacitance type input device of Example 1), and the capacitance type input by a known method. An image display device 1 of Example 1 including the device as a constituent element was produced.

<< Overall Evaluation of Front Plate 1 and Image Display Device 1 >>
In each of the above 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 was formed. The front plate 1 (capacitance type input device of Example 1) had no dirt on the opening and the back surface, was easily cleaned, and had no problem of contamination of other members.
In addition, the decorative layer had no pinholes, and there was no problem with whiteness and unevenness. Similarly, the mask layer had no pinholes and was excellent in light shielding properties.
And there is no problem in each conductivity of the first transparent electrode pattern, the second transparent electrode pattern, and the conductive element different from these, 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 bubbles and an image display device having excellent 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 in which 0.51 g of silver nitrate powder was dissolved in 50 mL of pure water was prepared. 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 became 100 mL, whereby an additive solution A was prepared.
In addition, 0.5 g of glucose powder was dissolved in 140 mL of pure water to prepare additive solution G.
Furthermore, 0.5 g of HTAB (hexadecyl-trimethylammonium bromide) powder was dissolved in 27.5 mL of pure water to prepare additive solution H.

Next, 20.6 mL of the additive solution A was placed in a three-necked flask and stirred at room temperature. Silver nanowire aqueous dispersion by adding 41 mL of pure water, 20.6 mL of additive solution H, and 16.5 mL of additive solution G to this solution with a funnel and heating at 90 ° C. for 5 hours with stirring at 200 rpm (1) was obtained.
After cooling the obtained silver nanowire aqueous dispersion (1), polyvinylpyrrolidone (trade name: K-30, manufactured by Wako Pure Chemical Industries, Ltd.) is adjusted to 0.05 with respect to the mass 1 of silver. Add with stirring, then centrifuge, purify until conductivity is below 50 μS / cm, further centrifuge with propylene glycol monomethyl ether to remove water, and finally add propylene glycol monomethyl ether. A silver nanowire solvent dispersion (1) was prepared.

(Preparation of coating liquid C1 for forming a conductive decorative layer)
The following composition was stirred and mixed with the silver nanowire dispersion (1) so 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 liquid C1 for forming conductive decorative layer-
-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 mass / surfactant (trade name: MegaFuck F-781F, manufactured by Dainippon Ink)
: 0.002 parts by mass / MMPGAc (manufactured by Daicel Chemical Industries): 19.3 parts by mass

<< Formation of transparent electrode pattern and insulating layer >>
In the same manner as in Example 1, after obtaining the front plate on which the decorative layer and the mask layer were formed, the conductive decorative layer forming coating liquid C1 was used instead of the photocurable resin layer coating liquid E1 for etching. The conductive decorative layer was laminated by the following procedure, and the first transparent electrode pattern was formed.
First, the front plate on which the decorative layer and the mask layer are formed is washed, and the coating liquid C1 for forming the conductive decorative layer is applied to the glass substrate coater (F-A) having a slit-like nozzle on the mask layer side of the front plate. -The coating liquid C1 for the said conductive decoration layer formation was apply | coated and dried by S Japan Co., Ltd. brand name: MH-1600), and the conductive decoration layer with a film thickness of 2.0 micrometers was obtained. The distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the conductive decorative layer was set to 100 μm, and pattern exposure was performed at an exposure amount of 100 mJ / cm ² (i-line).
Next, a sodium carbonate / sodium hydrogen carbonate developer (trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 5 times with pure water) at 25 ° C. for 60 seconds, surfactant-containing cleaning solution (Trade name: T-SD3 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) was treated at 33 ° C. for 20 seconds, and the residue was removed with a rotating brush and an ultra-high pressure washing nozzle. Furthermore, the post-baking process for 230 degreeC for 60 minutes was performed, and the front board in which the mask layer and the 1st transparent electrode pattern were formed was obtained.

Subsequently, an insulating layer was formed in the same manner as in Example 1. Subsequently, the electroconductive decoration layer was laminated | stacked similarly to formation of said 1st transparent electrode pattern in the present Example 2, and the 2nd transparent electrode pattern was formed. Further, 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, and the front plate 2 was obtained. This was the capacitive input device of Example 2.
In the same manner as in Example 1, an image display device 2 of Example 2 was produced.

<< Evaluation of Front Plate 2 and Image Display Device 2 >>
In each of the above 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 was formed. The front plate 2 had no dirt on the opening and the back surface, was easily cleaned, and had no problem of contamination of other members.
Also, the mask layer had no pinholes and was excellent in light shielding properties.
The first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements different from the first transparent electrode pattern have no problem with the respective conductivity, 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 bubbles and an image display device having excellent display characteristics was obtained.

[Examples 3 to 10]
Silicone resin KR300 (Example 3), Silicone resin KR282 (Example 4), Silicone resin KR300 without changing the solid content addition amount of the silicone resin in the heat-resistant decorative coloring composition of Example 1 (formulation L1) Solid content mixture of silicone resin KR282 (Example 5), Silicone resin KR271 (Example 6), Silicone resin KR255 (Example 7), Silicone resin KR212 (Example 8), Silicone resin KR9706 (Example 9) Preparation of a heat-resistant decorative coloring composition changed to silicone resin KR5230 (Example 10) (respectively referred to as prescriptions L3 to L10), respectively, as heat-resistant decorative coloring compositions of Examples 3 to 10, respectively. .
Example 1 except that the coloring composition for heat-resistant decoration of Examples 3 to 10 obtained instead of the coloring composition for heat-resistant decoration of Example 1 was used, that is, the binder shown in Table 1 below was changed. The front board which formed the decoration layer was produced similarly, and the result of having evaluated was described in following Table 1. Then, the electroconductive element different from a decoration layer, a mask layer, a 1st transparent electrode pattern, an insulating layer pattern, a 2nd transparent electrode pattern, and the 1st and 2nd transparent electrode pattern like Example 1. In addition, front plates 3 to 10 which are capacitive input devices of Examples 3 to 10 having a transparent protective layer formed thereon, and image display devices 3 to 10 including the capacitive input device as constituent elements were manufactured.
The front plates 3 to 10 were at practical levels in terms of brightness, whiteness, reticulation, yield, adhesion to the decorative layer, dirt on the openings, and missing openings.
Also, the mask layer had no pinholes and was excellent in light shielding properties.
The first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements different from the first transparent electrode pattern have no problem with the respective conductivity, 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 bubbles and an image display device having excellent display characteristics was obtained.

[Examples 11 to 13]
Instead of titanium oxide Ishihara Sangyo (CR97; alumina / zirconia treated rutile type, primary particle size 0.25 μm) used in the white pigment dispersion 1 used for the heat resistant decorative coloring composition (formulation L5) of Example 5 Ishihara Sangyo CR60 (alumina-treated rutile type, primary particle size 0.21 μm, Example 11), Ishihara Sangyo CR50 (alumina-treated rutile type, primary particle size 0.25 μm, Example 12), Ishihara Sangyo Prepared a color composition for heat-resistant decoration (respectively referred to as formulas L11 to L13) changed to CR58 (alumina-treated rutile type, primary particle size 0.28 μm, Example 13), and heat resistance of Examples 11 to 13 respectively. It was set as the coloring composition for sex decoration.
Front plate having a decorative layer formed in the same manner as in Example 5 except that the heat-resistant decorative coloring composition of Examples 11 to 13 was used instead of the heat-resistant decorative coloring composition of Example 5. Table 1 below shows the results of manufacturing and evaluation. Thereafter, in the same manner as in Example 5, 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 In addition, the front plates 11 to 13 as the capacitive input devices of Examples 11 to 13 and the transparent protective layer were formed, and the image display devices 11 to 13 including the capacitive input device as constituent elements were produced.
The front plates 11 to 13 had no problem with the dirt on the opening and the back surface, were easily cleaned, and had no problem with contamination of other members.
Also, the mask layer had no pinholes and was excellent in light shielding properties.
The first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements different from the first transparent electrode pattern have no problem with the respective conductivity, 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 bubbles and an image display device having excellent display characteristics was obtained.

[Examples 14 to 19]
20 mass parts (Example 14) and 26 mass parts (Example 15) from 44 mass parts, respectively, with respect to the total solid content by mass of the heat-resistant decorative coloring composition (Formulation L5) of Example 5. ), 32 parts by mass (Example 16), 36 parts by mass (Example 17), 60 parts by mass (Example 18), and 75 parts by mass (Example 19), respectively. Formulations L14 to L19) were prepared and used as the heat resistant decorative coloring compositions of Examples 14 to 19, respectively.
Front plate having a decorative layer formed in the same manner as in Example 5 except that the heat-resistant decorative coloring composition of Examples 14 to 19 was used instead of the heat-resistant decorative coloring composition of Example 5. Table 1 below shows the results of manufacturing and evaluation. Thereafter, in the same manner as in Example 5, 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 In addition, Examples 14 to 19 in which a transparent protective layer was formed Front plates 14 to 19 which are capacitive input devices, and image display devices 14 to 19 including the capacitive input device as constituent elements were produced.
From the results of Table 1 below, all evaluations were at a practical level within the range of 20 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 lack of the opening are slightly reduced, but at a practical level, whiteness, reticulation The dirt on the opening tended to improve. The lightness was in the best range of 38 to 60 parts by mass.
Also, the mask layer had no pinholes and was excellent in light shielding properties.
The first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements different from the first transparent electrode pattern have no problem with the respective conductivity, 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 bubbles and an image display device having excellent display characteristics was obtained.

[Examples 20 to 22]
In the coloring composition for heat-resistant decoration of Example 5 (formulation L5), phosphoric acid-based antioxidant IRGAFOS 168 (manufactured by BASF Japan, Example 20), phosphoric acid from phosphoric acid / hindered phenol-based antioxidant summizer GP, respectively. Coloring composition for heat-resistant decoration (respectively prescriptions) changed to a system antioxidant IRGAFOS38 (manufactured by BASF Japan, Example 21) and phosphoric acid / hindered phenol antioxidant IRGAMOD295 (manufactured by BASF Japan, Example 22) L20 to L22) were prepared and used as heat-resistant decorative coloring compositions of Examples 20 to 22, respectively.
Front plate having a decorative layer formed in the same manner as in Example 5 except that the heat-resistant decorative coloring composition of Examples 20 to 22 was used instead of the heat-resistant decorative coloring composition of Example 5. The results of evaluation are shown in Table 2 below. Thereafter, in the same manner as in Example 5, 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 Also, the front plates 20 to 22 which are the capacitance type input devices of Examples 20 to 22 formed with the transparent protective layer, and the image display devices 20 to 22 provided with the capacitance type input device as constituent elements were produced.
The front plates 20 and 21 were slightly improved in whiteness with respect to the front plate 5, and the others were equivalent and practical.
The evaluation result of the front plate 22 was the same as that of the front plate 5 with the same evaluation result.

[Examples 23 and 24]
In Example 5, using the coloring composition for heat-resistant decoration (formulation L5), the thickness of the decorative layer formed was changed from 36 μm (Example 5; 6 times printing application) to 18 μm (Example 23; 3 times printing application). ) Or 42 μm (Example 24; 7 times printing application), the decorative layer was formed in the same manner as in Example 5 except that the decorative layer of Examples 23 and 24 was formed, and the decorative layer was formed. The results of producing and evaluating the front plate are shown in Table 2 below. Thereafter, in the same manner as in Example 5, 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 In addition, the front plates 23 and 24, which are the capacitive input devices of Examples 23 and 24 in which the transparent protective layer was formed, and the image display device 23 including the capacitive input device as constituent elements were manufactured.
The front plates 23 and 24 have practical levels of brightness, whiteness, yield, reticulation, adhesion to the decorative layer, dirt on the opening, and missing openings on the front plate 5.
The front plates 23 and 24 had no problem with dirt on the opening and the back surface, were easily cleaned, and had no problem with contamination of other members.
Also, the mask layer had no pinholes and was excellent in light shielding properties.
The first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements different from the first transparent electrode pattern have no problem with the respective conductivity, 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 bubbles and an image display device having excellent display characteristics was obtained.

[Example 25]
In the coloring composition for heat-resistant decoration of Example 20 (formulation L20), an equivalent mixture of a silicone resin KR300 and a silicone resin KR311 having a solid content of 1/1 is used without changing the total solid content of the silicone resin. A heat-resistant decorative coloring composition (formulation L25) changed to Example 25) was prepared and used as the heat-resistant decorative composition of Example 25.
Before using the coloring composition L25 for heat-resistant decoration of Example 25, ie, changing to the binder shown in Table 2 below in the same manner as in Example 20 to form a decorative layer and forming a decorative layer The face plate was prepared and evaluated, and the results are shown in Table 2 below. Thereafter, in the same manner as in Example 20, 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 A front plate 25 that is a capacitive input device of Example 25 in which a transparent protective layer was formed, and an image display device 25 including the capacitive input device as constituent elements were produced.
The front plate 25 is at a practical level, although the whiteness, decoration layer adhesion, dirt on the opening, omission of the opening, and pre-cut suitability are deteriorated with respect to the front plate 20. Evaluation of brightness and yield reticulation is also possible. The result was comparable and practical.
The front plate 25 had no problem with dirt on the opening and the back surface, was easily cleaned, and had no problem with contamination of other members.
Also, the mask layer had no pinholes and was excellent in light shielding properties.
The first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements different from the first transparent electrode pattern have no problem with the respective conductivity, 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 bubbles and an image display device having excellent display characteristics was obtained.

[Example 26]
In the coloring composition for heat-resistant decoration of Example 25 (formulation L25), the coloring was performed by adding 4% by mass of a zinc resin condensation catalyst D-15 (manufactured by Shin-Etsu Chemical Co., Ltd.) of the total solid content of the silicone resin. The layer coating solution L26 was prepared as a heat resistant decorative coloring composition (formulation L26), and the heat resistant decorative coloring composition of Example 26 was prepared.
Except having used the coloring composition for heat resistant decoration of Example 26, it carried out similarly to Example 25, formed the decorating layer, produced the front board which formed the decorating layer, and evaluated the result below. 2. Thereafter, in the same manner as in Example 25, the electroconductive 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 In addition, a front plate 26 that is a capacitive input device of Example 26 in which a transparent protective layer was formed, and an image display device 26 including the capacitive input device as constituent elements were produced.
The front plate 26 is less than the front plate 25 in whiteness, decorative layer adhesion, dirt on the opening, and missing openings, but is at a practical level. In addition, the evaluation results of brightness and yield reticulation are the same. It was a practical level.
Also, the mask layer had no pinholes and was excellent in light shielding properties.
The first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements different from the first transparent electrode pattern have no problem with the respective conductivity, 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 bubbles and an image display device having excellent display characteristics was obtained.

[Examples 27 and 28]
In the heat-resistant decorative coloring composition of Example 26 (formulation L26), the solid content ratio of the silicone resin KR300 and the silicone resin KR311 was changed to 1/1 (implementation) without changing the total solid content addition amount of the silicone resin. Except for changing from Example 26) to 3/7 (Example 27) and 7/3 (Example 28), in the same manner as in Example 26, the heat-resistant decorative coloring composition of Examples 27 and 28 ( Preparations L27 and L28, respectively) were prepared and used as heat-resistant decorative coloring compositions of Examples 27 and 28.
Except having used the heat-resistant coloring composition of Example 27 and 28, it carried out similarly to Example 26, formed the decoration layer, produced the front board which formed the decoration layer, and evaluated the result. It described in Table 2 below. Thereafter, in the same manner as in Example 26, the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the conductive element different from the first and second transparent electrode patterns In addition, front plates 27 and 28, which are the capacitive input devices of Examples 27 and 28 in which a transparent protective layer was formed, and image display devices 27 and 28 having the capacitive input device as constituent elements were produced.
The front plates 27 and 28 were at a practical level in terms of transferability, pre-cut suitability, brightness, whiteness, reticulation, yield, decorative layer adhesion, opening dirt, and opening missing.
Also, the mask layer had no pinholes and was excellent in light shielding properties.
The first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements different from the first transparent electrode pattern have no problem with the respective conductivity, 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 bubbles and an image display device having excellent display characteristics was obtained.

[Examples 29 to 33]
In the coloring composition for heat-resistant decoration of Example 26 (formulation L26), the silicone resin KR400 (Example 29), the silicone resin KR500 (Example 30), and the silicone were added without changing the total solid content of the silicone resin. Solid content ratio of resin KR400 and silicone resin KR500 = 3/7 (Example 31), Solid content ratio of silicone resin KR400 and silicone resin KR500 = 7/3 (Example 32), Silicone resin KR400, Silicone resin KR500 and silicone A heat-resistant decorative coloring composition (Example 33) except that the solid content ratio of the alkoxy oligomer X-40-9225 was changed to 70/30 / 2.5 (Example 33). Preparations L29 to L33, respectively), and coloring for heat-resistant decoration of Examples 29 to 33, respectively It was formed products.
A decorative layer was formed in the same manner as in Example 26 except that the heat-resistant decorative coloring composition of Examples 29 to 33 was used instead of the heat-resistant decorative coloring composition of Example 26, respectively. Table 2 below shows the results of producing and evaluating a front plate on which a decorative layer was formed. Thereafter, in the same manner as in Example 26, the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the conductive element different from the first and second transparent electrode patterns In addition, front plates 29 to 33, which are the capacitance type input devices of Examples 29 to 33 having the transparent protective layer formed thereon, and image display devices 29 to 33 each including the capacitance type input device as constituent elements were produced.
The front plates 29 to 33 were at practical levels in terms of transferability, precut suitability, lightness, whiteness, reticulation, yield, decorative layer adhesion, dirt on openings, and missing openings.
Also, the mask layer had no pinholes and was excellent in light shielding properties.
The first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements different from the first transparent electrode pattern have no problem with the respective conductivity, 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 bubbles and an image display device having excellent display characteristics was obtained.

[Examples 34 to 39]
In the coloring composition for heat-resistant decoration of Example 26 (Formulation L26), the type of silicone resin was changed to the toluene solution of Example 1 (Example 34; methyl tolyl) without changing the total solid content of the silicone resin. Type silicone resin), toluene solution of the condensate of Synthesis Example 2 (Example 35; methyl benzyl type silicone resin), toluene solution of the condensate of Synthesis Example 3 (Example 36; methyl cumyl type silicone resin), synthesis The toluene solution of the condensate of Example 4 (Example 37; ethyl tolyl type silicone resin), the toluene solution of the condensate of Synthesis Example 5 (Example 38; propyl tolyl type silicone resin), and the condensate of Synthesis Example 6 Except for changing to a toluene solution (Example 39; methyl hydride type silicone resin), the same color assembly for heat-resistant decoration as in Example 26. Compositions (prepared as L34 to L39, respectively) were prepared and used as the heat resistant decorative coloring compositions of Examples 34 to 39, respectively.
A decorative layer was formed in the same manner as in Example 26 except that the heat-resistant decorative coloring composition of Examples 34 to 39 was used instead of the heat-resistant decorative coloring composition of Example 26, respectively. Table 2 below shows the results of producing and evaluating a front plate on which a decorative layer was formed. Thereafter, in the same manner as in Example 26, the decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the conductive element different from the first and second transparent electrode patterns In addition, front plates 34 to 39, which are capacitive input devices of Examples 34 to 39 in which a transparent protective layer was formed, and image display devices 34 to 39 including the capacitive input device as constituent elements were produced.
The front plates 34 to 39 were at practical levels in terms of brightness, whiteness, reticulation, yield, adhesion to the decorative layer, dirt on the openings, and missing openings.
Also, the mask layer had no pinholes and was excellent in light shielding properties.
The first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements different from the first transparent electrode pattern have no problem with the respective conductivity, 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 bubbles and an image display device having excellent display characteristics was obtained.

[Examples 40 and 41]
In the coloring composition for heat-resistant decoration of Example 1 (formulation L1), the silicone resin KR251 (Example 40), the silicone resin KR251, and X-40- Heat-resistant in the same manner as in Example 1 except that the colored layer coating liquids L43 and 44 were changed to a 9246 solid content 9/1 mixture (Example 41), that is, changed to the binder shown in Table 2 below. Coloring compositions for decoration (referred to as formulations L40 and L41, respectively) were prepared and used as the heat-resistant coloring compositions for Examples 40 and 41, respectively.
A decorative layer is formed in the same manner as in Example 1, except that the heat-resistant decorative coloring composition of Examples 40 and 41 is used instead of the heat-resistant decorative coloring composition of Example 1, respectively. The front plate on which the decorative layer was formed was prepared and evaluated, and the results are shown in Table 2 below. Then, the electroconductive element different from a decoration layer, a mask layer, a 1st transparent electrode pattern, an insulating layer pattern, a 2nd transparent electrode pattern, and the 1st and 2nd transparent electrode pattern like Example 1. In addition, front plates 40 and 41, which are the capacitance type input devices of Examples 40 and 41 having the transparent protective layer formed thereon, and image display devices 40 and 41 having the capacitance type input device as constituent elements were produced.
Compared to the front plate 1, the front plates 40 and 41 have significantly improved brightness, and transferability, precut suitability, whiteness, reticulation, yield, adhesion to the decorative layer, opening dirt, and missing openings are practical. It was a level.
Also, the mask layer had no pinholes and was excellent in light shielding properties.
The first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements different from the first transparent electrode pattern have no problem with the respective conductivity, 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 bubbles and an image display device having excellent display characteristics was obtained.

[Comparative Example 1]
In the coloring composition for heat-resistant decoration of Example 1 (formulation L1), the following polyamic acid (described as polyimide in Table 2 below) is added in place of the silicone resin KR-311, and the same solid content is added. A colored composition (Formulation L51) was obtained. The obtained coloring composition for heat-resistant decoration was used as the coloring composition for heat-resistant decoration of Comparative Example 1.

(Polymerization of polyimide precursor polyamic acid)
Into a reaction vessel, 210 parts by mass of 4,4′-methylenebis (cyclohexylamine) was dissolved in 2860 parts by mass of N-methyl-2-pyrrolidone, and then pyromellitic dianhydride powder 218 with stirring in a nitrogen stream. Mass parts were gradually added and reacted at 35 ° C. for 8 hours to obtain a transparent and viscous polyamic acid solution.

Except having used coloring composition prescription L51 for the heat resistant decoration of the comparative example 1, it forms the front board 51 which formed the decorating layer on the tempered glass similarly to Example 1, and after baking to 350 degreeC The temperature was raised in about 20 seconds, and heat treatment was performed at 350 ° C. for 7 minutes to complete imidization of the polyamic acid.
Then, the electroconductive element different from a decoration layer, a mask layer, a 1st transparent electrode pattern, an insulating layer pattern, a 2nd transparent electrode pattern, and the 1st and 2nd transparent electrode pattern like Example 1. In addition, a front plate 51 which is a capacitance type input device of Comparative Example 1 in which a transparent protective layer is formed, and an image display device 51 including the capacitance type input device as a constituent element are manufactured and evaluated. 2.
The front plate 51 was markedly reduced in whiteness, decorating layer adhesion, lack of openings, and yield with respect to the front plate 1 and became NG level. There was no problem with the contamination of the opening and the back surface, the cleaning was easy, 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.
The first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements different from the first transparent electrode pattern have no problem with the respective conductivity, 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 bubbles and an image display device having excellent display characteristics was obtained.

[Comparative Example 2]
Instead of silicone resin KR-311 in the coloring composition for heat-resistant decoration of Example 1 (prescription L1), an acrylic binder 1 (random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, weight average molecular weight 3 70,000, described as “acrylic” in Table 2 below) was added in the same solid content to obtain a heat-resistant colored composition for decoration (prescription L52). The obtained heat resistant decorative coloring composition was used as the heat resistant decorative composition of Comparative Example 2.
The decorative layer, the mask layer, the first transparent electrode pattern, the insulating layer pattern, the second layer are the same as in Example 1 except that the coloring composition for heat-resistant decoration (Prescription L52) of Comparative Example 2 is used. Front plate 52, which is a capacitive input device of Comparative Example 2, in which a transparent electrode pattern, a conductive element different from the first and second transparent electrode patterns, and a transparent protective layer are formed, and a capacitive input device Table 2 below shows the results of producing and evaluating the image display device 52 including the above as constituent elements.
With respect to the front plate 52, the whiteness, the decorative layer adhesion, the lack of the opening, and the yield of the front plate 52 were remarkably lowered and became NG level. There was no problem with the contamination of the opening and the back surface, the cleaning was easy, and there was no problem of contamination of other members.
Further, the front plate 52 has no pinhole in the mask layer and has excellent light shielding properties.
The first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements different from the first transparent electrode pattern have no problem with the respective conductivity, 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 bubbles and an image display device having excellent display characteristics was obtained.

From Table 1 and Table 2, by using the coloring composition for heat-resistant decoration of the present invention, a white decorative layer having good brightness, whiteness, reticulation and adhesion after transfer has a high yield. Further, as described above, according to the method for manufacturing a capacitance-type input device of the present invention using the coloring composition for heat-resistant decoration of the present invention, thin layer / weight reduction Capacitance type input device that has the following advantages can be manufactured with high quality in a simple process. For this reason, it turns out that the electrostatic capacitance type input device manufactured with the manufacturing method of this invention, and an image display apparatus using the same are high quality.
In addition, according to the more preferable aspect of the manufacturing method of the capacitance-type input device of the present invention, it was found that even when a substrate having an opening is used, the protrusion of the resist and the contamination on the back side of the substrate are small.

DESCRIPTION OF SYMBOLS 1 Front plate 1a Non-contact side 2a of front plate Decorating layer 2b Mask layer 3 1st transparent electrode pattern 3a Pad part 3b Connection part 4 2nd transparent electrode pattern 5 Insulating layer 6 Conductive element 7 Transparent protective layer 8 Opening Part 10 Capacitive type input device 11 Tempered glass 12 Another conductive element 13 Antifouling plate 14 Antifouling plug C First direction D Second direction

Claims (27)

See contains at least (A) an organic pigment and (B) a silicone-based resin,
The heat-resistant decorative coloring composition, wherein the silicone resin contains a straight silicone resin containing at least a siloxane structure represented by the following general formula (1) in the molecule .
General formula (1)

(In general formula (1), R ¹ is independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic group having 1 to 6 carbon atoms. A substituted alkyl group or an aryl group having 6 to 9 carbon atoms)   The coloring composition for heat-resistant decoration according to claim 1, wherein the coloring composition for decoration further contains (C) an antioxidant. In the said General formula (1), R < ¹ > represents a hydrogen atom, a methyl group, or a tolyl group independently, The coloring composition for heat resistant decorations of Claim 1 or 2 characterized by the above-mentioned. Heat resistance pressure according to any one of claims 1 to 3, wherein the white inorganic pigment content of respect to the total solid content of the heat-resistant decorative coloring composition is 20 to 75 wt% Coloring composition for decoration. The said white inorganic pigment is a rutile type titanium oxide surface-treated with an inorganic substance, The heat-resistant coloring composition for decorating as described in any one of Claims 1-4 characterized by the above-mentioned. The coloring composition for heat resistant decoration according to claim 5 , wherein the rutile type titanium oxide is a rutile type titanium oxide surface-treated with at least one of alumina and zirconia. The coloring composition for heat-resistant decoration according to any one of claims 1 to 6 , wherein the coloring composition for heat-resistant decoration is used for decorating a capacitance type input device front panel. . A method for manufacturing a capacitive input device having a front plate and at least the following elements (1) and (3) to (5) on the non-contact side of the front plate:
Applying the coloring composition for heat-resistant decoration according to any one of claims 1 to 7 to the non-contact side of the front plate to include at least the step (1) of forming a decoration layer. A method for 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 via connecting portions (4) The first transparent electrode pattern and A plurality of second electrode patterns comprising a plurality of pad portions that are electrically insulated and extend in a direction intersecting the first direction. (5) The first transparent electrode pattern and the second electrode pattern. Insulating layer that electrically insulates the electrode pattern   A method for manufacturing a capacitive input device having a front plate and at least the following elements (1) and (3) to (5) on the non-contact side of the front plate:
  Including a step of applying at least (1) a decorative layer by applying a heat resistant decorative coloring composition containing at least (A) a white inorganic pigment and (B) a silicone resin to the non-contact side of the front plate. ,
  (1) A method for manufacturing a capacitance-type input device, further comprising: (2) providing a mask layer on a surface of the decorative layer opposite to the front plate.
(1) Decorative layer
(3) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in the first direction via the connection portions.
(4) A plurality of second electrode patterns comprising a plurality of pad portions that are electrically insulated from the first transparent electrode pattern and extend in a direction intersecting the first direction.
(5) An insulating layer for electrically insulating the first transparent electrode pattern and the second electrode pattern   A method for manufacturing a capacitive input device having a front plate and at least the following elements (1) and (3) to (5) on the non-contact side of the front plate:
  Including a step of applying at least (1) a decorative layer by applying a heat resistant decorative coloring composition containing at least (A) a white inorganic pigment and (B) a silicone resin to the non-contact side of the front plate. ,
  The method of manufacturing a capacitive input device, wherein the front plate has an opening at least in part.
(1) Decorative layer
(3) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in the first direction via the connection portions.
(4) A plurality of second electrode patterns comprising a plurality of pad portions that are electrically insulated from the first transparent electrode pattern and extend in a direction intersecting the first direction.
(5) An insulating layer for electrically insulating the first transparent electrode pattern and the second electrode pattern 11. The capacitive input device according to claim 8 , further comprising (2) a mask layer provided on a surface of the decorative layer opposite to the front plate. Method. At least one of the first transparent electrode pattern and the second electrode pattern is disposed across both the non-contact surface of the front plate and the region of the mask layer on the side opposite to the front plate. The method for manufacturing a capacitance-type input device according to claim 9 or 11 . The capacitive input device is further (6) electrically connected to at least one of the first transparent electrode pattern and the second electrode pattern, and the first transparent electrode pattern and the second electrode. Having conductive elements separate from the pattern,
The electrostatic conductivity according to any one of claims 9, 11 and 12, wherein the (6) another conductive element is disposed at least on a surface side opposite to the front plate of the mask layer. A method for manufacturing a capacitive input device. The method for manufacturing a capacitive input device according to any one of claims 8, 9, and 11 to 13 , wherein the front plate has an opening at least partially. The capacitive input device is further (6) electrically connected to 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 for manufacturing a capacitive input device according to claim 8, further comprising a conductive element different from the pattern. The method for manufacturing a capacitive input device according to claim 8, wherein the second electrode pattern is a transparent electrode pattern. The thickness of the said decoration layer is 1-40 micrometers, The manufacturing method of the electrostatic capacitance type input device as described in any one of Claims 8-16 characterized by the above-mentioned. (1) The decorative layer is heated to 180 to 300 ° C. in an environment of 0.08 to 1.2 atm after applying the coloring composition for heat resistant decoration to the non-contact side of the front plate. It forms, The manufacturing method of the electrostatic capacitance type input device as described in any one of Claims 8-17 characterized by the above-mentioned. The method for manufacturing a capacitive input device according to claim 18 , wherein the decoration layer is heated in an air environment. Applying the heat-resistant decorative coloring composition in a non-contact side of the front plate, one of the claims 8 to 19, characterized in that the step of printing the heat-resistant decorative coloring composition A method for manufacturing the capacitive input device according to claim 1. Furthermore, a transparent protective layer is installed so that all or a part of said (1) and (3)-(5) element may be covered, The static as described in any one of Claims 8-20 characterized by the above-mentioned. A method for manufacturing a capacitive input device. The method for manufacturing a capacitive input device according to claim 21 , wherein the transparent protective layer is formed using a curable resin composition. The capacitive input device is further (6) electrically connected to at least one of the first transparent electrode pattern and the second electrode pattern, and the first transparent electrode pattern and the second electrode. Having conductive elements separate from the pattern,
The second electrode pattern is a transparent electrode pattern;
Etching the transparent conductive material using the etching pattern formed by the curable resin composition, the (3) first transparent electrode pattern, the (4) second transparent electrode pattern, and the (6) conductive element. It forms by processing, The manufacturing method of the electrostatic capacitance type input device of any one of Claims 8-22 characterized by the above-mentioned. The capacitive input device is further (6) electrically connected to at least one of the first transparent electrode pattern and the second electrode pattern, and the first transparent electrode pattern and the second electrode. Having conductive elements separate from the pattern,
The second electrode pattern is a transparent electrode pattern;
At least one of the (3) first transparent electrode pattern, the (4) second transparent electrode pattern, and the (6) conductive element is formed using a conductive curable resin composition. The method for manufacturing a capacitance-type input device according to any one of claims 8 to 22 . Surface treatment is performed on the non-contact surface of the front plate,
The method for manufacturing a capacitive input device according to any one of claims 8 to 24 , wherein a curable resin composition is placed on a non-contact surface of the front plate subjected to the surface treatment. . 26. The method of manufacturing a capacitive input device according to claim 25 , wherein a silane compound is used for the surface treatment of the front plate. 27. A method for manufacturing an image display device , comprising the method for manufacturing a capacitance-type input device according to any one of claims 8 to 26 .

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